CN108409574A - A kind of citrate and its preparation method and application - Google Patents
A kind of citrate and its preparation method and application Download PDFInfo
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- CN108409574A CN108409574A CN201810339150.3A CN201810339150A CN108409574A CN 108409574 A CN108409574 A CN 108409574A CN 201810339150 A CN201810339150 A CN 201810339150A CN 108409574 A CN108409574 A CN 108409574A
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- Prior art keywords
- citrate
- toy
- pvc paste
- water
- deaeration
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 238000001816 cooling Methods 0.000 claims description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 40
- 229910052802 copper Inorganic materials 0.000 claims description 40
- 239000010949 copper Substances 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- 239000003381 stabilizer Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 239000003549 soybean oil Substances 0.000 claims description 21
- 235000012424 soybean oil Nutrition 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 239000004922 lacquer Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000004042 decolorization Methods 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 150000001860 citric acid derivatives Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007592 spray painting technique Methods 0.000 abstract description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 63
- 239000004800 polyvinyl chloride Substances 0.000 description 63
- 239000004014 plasticizer Substances 0.000 description 32
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 21
- 238000007493 shaping process Methods 0.000 description 16
- 235000015165 citric acid Nutrition 0.000 description 14
- 238000010422 painting Methods 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 9
- 235000005979 Citrus limon Nutrition 0.000 description 6
- 244000131522 Citrus pyriformis Species 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 238000010183 spectrum analysis Methods 0.000 description 4
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 3
- -1 citric acid ester Chemical class 0.000 description 3
- 239000004806 diisononylester Substances 0.000 description 3
- PESZCXUNMKAYME-UHFFFAOYSA-N Citroflex A-4 Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)C(C(C)=O)C(=O)OCCCC PESZCXUNMKAYME-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 2
- 239000001069 triethyl citrate Substances 0.000 description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 2
- 235000013769 triethyl citrate Nutrition 0.000 description 2
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- 206010001606 Alcohol problem Diseases 0.000 description 1
- 101100325962 Arabidopsis thaliana BHLH80 gene Proteins 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000008037 PVC plasticizer Substances 0.000 description 1
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 208000028505 alcohol-related disease Diseases 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- AMMPRZCMKXDUNE-UHFFFAOYSA-N trihexyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(O)(C(=O)OCCCCCC)CC(=O)OCCCCCC AMMPRZCMKXDUNE-UHFFFAOYSA-N 0.000 description 1
- DXRFOGXSSDRZFP-UHFFFAOYSA-N tripentyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical class CCCCCOC(=O)CC(O)(C(=O)OCCCCC)CC(=O)OCCCCC DXRFOGXSSDRZFP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of citrates and its preparation method and application.The present invention solves the problems, such as that the toy spray painting rear surface stickness of existing citrate production generates the citrate that average molecular weight is 379.12~416.53 under the effect of the catalyst using citric acid, isobutanol and octanol as raw material；Above-mentioned citrate is neutralized, washing, rectifying, decoloration, obtains purity up to 99.5% or more citrate after filtering.Invention also provides its applications in toy preparation.It the method can be widely used in toy production field.
Description
Technical field
The present invention relates to a kind of plasticizer and its preparation method and application, specifically a kind of lemon suitable for toy
Acid ester plasticizer and its preparation method and application.
Background technology
Citrate is citric acid and alcohol is generated through esterification under the effect of the catalyst one kind is environment-protecting and non-poisonous can
Degradation plasticizer.Currently, citric acid ester plasticizer mainly has triethyl citrate (TEC), acetyl triethyl citrate
(ATEC), tributyl citrate (TBC), tributyl 2-acetylcitrate (ATBC), citric acid tri-n-hexyl ester (THC), acetyl lemon
Sour three just own esters (ATHC), trioctyl lemon acid (TOC), acetyl tributyl citrate (ATOC) etc..Wherein tributyl citrate
(TBC), tributyl 2-acetylcitrate (ATBC) and the compatibility of polyvinyl chloride resin are good, and plasticizing efficiency is high, and application is relatively broad.
Currently, European Union's EN71 toys standards, U.S.'s ASTM F963-08 Toy Safety Standards have limited adjacent benzene class plasticizer
Use, Chinese toy newly marks《GB6675-2014》In on January 1st, 2016 formally implement, it is specified that：In all toys,
Total content≤0.1% of tri- kinds of plasticizer of DEHP, DBP and BBP, the tri- kinds of plasticising of toy DINP, DIDP, DNOP that can be put into mouth
Total content≤0.1% of agent.In addition, China is as maximum PVC toys exports state in the world, there is an urgent need for environment-friendly plasticizers to replace passing
System plasticizer, meets the requirement of products export.The common environment-friendly plasticizer of toy product has BASF DINCH, South Korea on the market
GL300, TBC, ATBC etc., wherein BASF DINCH and South Korea GL300 plasticizer prices are high, and only a small number of producers are with lacking
Widely available property；TBC plasticizer are easily precipitated, stickness, anti-pollution characteristic are poor after made toy surface lacquer；ATBC plasticizer be through
The product that TBC acetylations obtain, though performance makes moderate progress, still remaining surface when manufacturing hardness and being less than the toy of 75A sprays
The problem of stickness after paint, anti-pollution characteristic difference, affects the storage and use of toy.
The Chinese invention patent application of Publication No. CN 101085736A discloses a kind of tripentyl citrates as PVC
The technical solution of plasticizer, but amylalcohol low output, price are high at present, can neither meet the needs of high-volume industry plasticizer,
Cause the increase of use cost.
The synthetic method of trioctyl lemon acid disclosed in the Chinese invention patent application of Publication No. CN 101245008A and
Skill of the three palm ester of citric acid as PVC plasticizer disclosed in the Chinese invention patent application of Publication No. CN 102643198A
Art scheme, though the trioctyl lemon acid and the three palm ester of citric acid have resistance to migration, plasticizing efficiency poor, viscous
Degree is high, is not suitable for the processing that PVC wards off glue type toy.
The Chinese patent of patent No. CN 103113617B discloses a kind of plasticizer and preparation method thereof, mainly passes through
It is low intolerant to migration, volatilization and citric acid higher alcohols plasticizing efficiency that citric acid reacts solution lemon acid low carbon alcohol ester with high-low carbon alcohol
Problem, but cannot solve the problems, such as that the plasticizer is applied in toy and cause surface tack.
Invention content
The present invention be exactly in order to solve the toy spray painting rear surface stickness for the production of existing citrate, be stained with ash, intolerant to
Dirty problem, provides a kind of environment-protecting and non-poisonous degradable citrate plasticizer and its preparation method and application.
The present invention passes through one step system of esterification under the effect of the catalyst using citric acid, isobutanol and octanol as raw material
；Obtained citrate after the purification operations such as neutralized, washing, rectifying, decoloration, filtering again after the completion of esterification.
The present invention provides a kind of preparation processes of citrate, include the following steps：(1) it is esterified：By citric acid, isobutyl
In alcohol, octanol and catalyst input reaction kettle of the esterification, agitating and heating weighs the water generated in record phase separator, waits for water yield
When reaching theoretical value, then 0.5~1.5h of isothermal reaction is measured by sampling and records acid value, and cooling discharge is to neutralizing kettle；(2) alkali
It washes：According to load and acid value, sodium hydroxide solution is configured, with 10%~20% alkali liquid washing of quality of material number to be neutralized
Once, it maintains temperature between 70~72 DEG C, stirs 20~40 minutes, constant temperature stands 1~1.25h, divides sub-cloud waste water；(3)
Washing：The temperature in step (2) is maintained, is washed twice with 10%~20% softened water of material mass number to be washed, every time
Stirring 20~40 minutes, constant temperature stand 1~1.25h, divide sub-cloud waste water；(4) rectification and purification：The method for taking vacuum distillation,
Negative pressure maintains -0.095~-0.1Mpa, and temperature is maintained at 138~140 DEG C, and the material after washing in step (3) is persistently pumped
Enter rectifying column, to remove extra alcohol and fail the water divided completely；(5) decolorization filtering：By the material after rectifying in step (4)
It is pumped into decoloration kettle, the activated carbon for waiting for decolorization material mass number 0.25%~0.75% is added, temperature is kept to stablize at 78~80 DEG C
Between, stirring 20~be pumped into filter progress press filtration after forty minutes, to obtain purity up to 99.5% or more citrate.
Preferably, in step (1), using citric acid, isobutanol and 2-Ethylhexyl Alcohol as reaction raw materials.The isobutanol and
The molar ratio of the 2-Ethylhexyl Alcohol is 1:0.125~0.5.
Preferably, in step (1), the citrate average molecular weight is 379.12~416.53.
Preferably, the citrate at least contains two or more compound, and molecular formula is as follows：
Preferably, group R in the compound molecule formula that the citrate includes1、R2And R3For different carbon atom numbers
Alkyl, group R1、R2And R3It is the one or two kinds of of C4, C8 aliphatic alkyl, group R4For one kind of H or carboxylic acid group.
Preferably, in the alkyl for the compound molecule formula that the citrate includes, C4 is isobutyl group, and C8 includes just pungent
Base and 2- ethylhexyls.
Present invention simultaneously provides a kind of application of citrate in toy, it is characterised in that including following parts by weight
Component：
Preferably, the PVC paste resin polymerization degree 1200~1500；The PVC suspending resins degree of polymerization 900~1000；
The thinner is 2,2,4- trimethyls 1, the double isobutyrates of 3- pentanediols；The stabilizer is liquid calcium zinc stabilizer；It is described
Auxiliary stabilizer is the epoxidized soybean oil that epoxide number is more than 6.0；The releasing agent is methyl-silicone oil.
A kind of application of the citrate of the present invention in toy, includes the following steps：
(1) dispensing：It is stirred after citrate of the present invention is mixed with epoxidized soybean oil, stabilizer, puts into PVC paste
Resin, PVC suspending resins, thinner, releasing agent, are uniformly mixing to obtain PVC paste material；
(2) deaeration：By PVC paste material deaeration made from step (1)；
(3) enter mould：PVC paste material made from step (2) is poured into copper mould；
(4) it heats：It step (3) copper mould is put into revolution wards off in glue stove and heat；
(5) cooling：Copper after step (4) is heated has recirculated water cooling, and toy product is made to shape；
(6) it molds：Toy die sinking made from step (5) is taken out；
(7) it paints：The toy that step (6) is taken out is made after being painted to appointed part with environment-friendly water-based or oiliness toy lacquer
Finished product.
Preferably, step (2) deaeration condition is 0.06~0.09MPa.
Preferably, heating condition is 250~300 DEG C in step (4), 5~8min.
The isobutanol that non-straight chain structure is introduced in the citrate molecular structure of the present invention replaces the n-butanol of linear chain structure,
Make to form methylic short-chain branch in molecular structure, while the 2-Ethylhexyl Alcohol for introducing higher alcohols improves molecular weight, it not only can be with
The viscosity stability for improving PVC paste material in use, can also improve product resistance to migration.
The toy spray of the citrates such as existing TBC, ATBC production can be solved in the toy of the citrate production of the present invention
Paint rear surface stickness is stained with the shortcomings that ash, not resistant.
The citrate of the present invention is greatly reduced compared with environment-friendly plasticizers costs such as BASF DINCH, South Korea GL300, and point
It is entirely free of benzene ring structure in son, meets the newest toys standard of European Union, the U.S. and China etc..
Specific implementation mode
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without this hair described in claims should will not be limited
It is bright.
Embodiment 1
The preparation process of citrate is as follows：
(1) esterification：By 120g anhydrous citric acids, 124.46g isobutanols, 100.32g octanols, 1g catalyst, in ester
Change in reaction kettle, agitating and heating weighs and record the water generated in phase separator, and when water yield reaches theoretical value, constant temperature is anti-
It answers 30 minutes, is measured by sampling and records acid value, cooling discharge is to neutralizing kettle.
(2) alkali cleaning：According to load and acid value, sodium hydroxide solution is configured, temperature is maintained to stablize between 70 DEG C, with waiting for
10% alkali liquid washing for neutralizing material mass number is primary, stirs 20 minutes, and constant temperature stands 60 minutes, divides sub-cloud waste water.
(3) it washes：Temperature is maintained to stablize between 70 DEG C, with 10% softening water washing two of material mass number to be washed
Secondary, stirring 20 minutes, constant temperature stand 60 minutes, divide sub-cloud waste water every time.
(4) rectification and purification：The method for taking vacuum distillation, negative pressure maintain -0.095Mpa, and temperature is maintained at 138 DEG C, will
Material after washing is persistently pumped into rectifying column, to remove extra alcohol and fail the water divided completely.
(5) decolorization filtering：Material after rectifying is pumped into decoloration kettle, and 0.75% activity for waiting for decolorization material mass number is added
Charcoal maintains 80 DEG C of temperature, stirring to be pumped into filter after twenty minutes and carry out press filtration, citrate is made after press filtration.Through gas phase color
Spectrum analysis, finished product ester content is up to 99.75%.
Embodiment 2
The preparation process of citrate is as follows：
(1) esterification：By 120g anhydrous citric acids, 138.57g isobutanols, 91.05g octanols, 1g catalyst is being esterified
In reaction kettle, agitating and heating weighs and records the water generated in phase separator, when water yield reaches theoretical value, isothermal reaction
90 minutes, it is measured by sampling and records acid value, cooling discharge is to neutralizing kettle.
(2) alkali cleaning：According to load and acid value, sodium hydroxide solution is configured, temperature is maintained to stablize between 72 DEG C, with waiting for
20% alkali liquid washing for neutralizing material mass number is primary, and constant temperature stands 1.25h, divides sub-cloud waste water.
(3) it washes：72 DEG C are maintained the temperature at, is washed twice with 20% softened water of material mass number to be washed, every time
Stirring 40 minutes, constant temperature stand 1.25h, divide sub-cloud waste water.
(4) rectification and purification：The method for taking vacuum distillation, negative pressure maintain -0.095Mpa, and temperature is maintained at 139 DEG C, will
Material after washing is persistently pumped into rectifying column, to remove extra alcohol and fail the water divided completely.
(5) decolorization filtering：Material after rectifying is pumped into decoloration kettle, and 0.25% activity for waiting for decolorization material mass number is added
Charcoal maintains 79 DEG C of temperature, stirring to be pumped into filter after forty minutes and carry out press filtration, citrate is made after press filtration.Through gas phase color
Spectrum analysis, finished product ester content is up to 99.75%.
Embodiment 3
The preparation process of citrate is as follows：
(1) esterification：By 120g anhydrous citric acids, 157.21g isobutanols, 47.65g octanols, 1g catalyst is being esterified
In reaction kettle, agitating and heating weighs and records the water generated in phase separator, when water yield reaches theoretical value, isothermal reaction
1h, is measured by sampling and records acid value, and cooling discharge is to neutralizing kettle.
(2) alkali cleaning：According to load and acid value, sodium hydroxide solution is configured, maintains temperature to stablize at 71 DEG C, use is to be neutralized
15% alkali liquid washing of quality of material number is primary, and constant temperature stands 68min, divides sub-cloud waste water.
(3) it washes：70 DEG C are maintained the temperature at, is washed twice with 15% softened water of material mass number to be washed, every time
0.5h is stirred, constant temperature stands 68min, divides sub-cloud waste water.
(4) rectification and purification：The method for taking vacuum distillation, negative pressure maintain -0.1Mpa, and temperature is maintained at 139 DEG C, by water
Material after the completion of washing persistently is pumped into rectifying column, to remove extra alcohol and fail the water divided completely.
(5) decolorization filtering：Material after rectifying is pumped into decoloration kettle, and 0.5% work for waiting for decolorization material mass number is added
Property charcoal, maintain 80 DEG C of temperature, stir and be pumped into filter after 0.5h and carry out press filtration, citrate is made after press filtration.Through gas phase color
Spectrum analysis, finished product ester content is up to 99.75%.
The preparation process of 4 citric acid fat of embodiment is as follows：
(1) esterification：By 120g anhydrous citric acids, 163.21g isobutanols, 41.84g octanols, 1g catalyst is being esterified
In reaction kettle, agitating and heating weighs and records the water generated in phase separator, when water yield reaches theoretical value, isothermal reaction
75 minutes, it is measured by sampling and records acid value, cooling discharge is to neutralizing kettle.
(2) alkali cleaning：According to load and acid value, sodium hydroxide solution is configured, maintains temperature to stablize at 70 DEG C, use is to be neutralized
18% alkali liquid washing of quality of material number is primary, stirs 25 minutes, and constant temperature stands 1h, divides sub-cloud waste water.
(3) it washes：70 DEG C are maintained the temperature at, is washed twice with 18% softened water of material mass number to be washed, every time
Stirring 25 minutes, constant temperature stand 1h, divide sub-cloud waste water.
(4) rectification and purification：The method for taking vacuum distillation, negative pressure maintain -0.1Mpa, and temperature is maintained at 139 DEG C, by water
Material after washing persistently is pumped into rectifying column, to remove extra alcohol and fail the water divided completely.
(5) decolorization filtering：Material after rectifying is pumped into decoloration kettle, and 0.6% activity for waiting for decolorization material mass number is added
Charcoal maintains 80 DEG C of temperature, stirring to be pumped into filter after 35 minutes and carry out press filtration, citrate is made after press filtration.Through gas phase color
Spectrum analysis, finished product ester content is up to 99.75%.
The physical function parameter of citrate obtained by table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Average molecular weight | 413.56 | 402.16 | 385.24 | 379.58 |
| Density (g/cm3, 25 DEG C) | 1.021 | 1.025 | 1.028 | 1.031 |
| Platinum-cobalt method coloration (#) | 30 | 25 | 20 | 20 |
| Viscosity (mPas, 25 DEG C) | 65 | 60 | 56 | 53 |
| Acid value (mgKOH/g, %) | 0.10 | 0.09 | 0.08 | 0.08 |
| Ester content (%) | 99.71 | 99.75 | 99.78 | 99.76 |
| Water content (%) | 0.07 | 0.07 | 0.07 | 0.07 |
| Flash-point (DEG C, open cup) | 191 | 190 | 187 | 185 |
Experimental example 5
Application of the citrate of the present invention in toy, steps are as follows：
70g citrate plasticizers obtained in embodiment 1 and 8g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 80gPVC pastes resin, 20gPVC suspending resins, 8g thinners, 0.6g releasing agents, is uniformly mixing to obtain PVC paste material；It will be above-mentioned
Deaeration under the conditions of 0.06MPa of PVC paste material；PVC paste material is poured into copper mould after deaeration；Copper mould is put into revolution and wards off glue
Stove toasts 8min under conditions of 250 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Environment-protective water will be used
Property or oiliness toy lacquer to appointed part paint after obtain finished product.
Embodiment 6
Application of the citrate of the present invention in toy, steps are as follows：
100g citrate plasticizers obtained in embodiment 1 and 8g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 95gPVC pastes resin, 5gPVC suspending resins, 5g thinners, 0.8g releasing agents, is uniformly mixing to obtain PVC paste material；It will be above-mentioned
Deaeration under the conditions of 0.06MPa of PVC paste material；PVC paste material is poured into copper mould after deaeration；Copper mould is put into revolution again and wards off glue
Stove toasts 8min under conditions of 250 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Using environment-friendly water-based
Or oiliness toy lacquer after appointed part spray painting to obtaining finished product.
Embodiment 7
Application of the citrate of the present invention in toy, steps are as follows：
120g citrate plasticizers obtained in embodiment 1 and 6g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 100gPVC pastes resin, 5g thinners, 1g releasing agents, is uniformly mixing to obtain PVC paste material；Above-mentioned PVC paste material is existed
Deaeration under the conditions of 0.06MPa；PVC paste material is poured into copper mould after deaeration；Copper mould is put into revolution and wards off glue stove again, at 250 DEG C
Under conditions of toast 8min；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Use environment-friendly water-based or oiliness toy
Paint obtains finished product after painting to appointed part.
Embodiment 8
Application of the citrate of the present invention in toy, steps are as follows：
70g citrate plasticizers obtained in embodiment 2 and 8g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 80gPVC pastes resin, 20gPVC suspending resins, 8g thinners, 0.6g releasing agents, is uniformly mixing to obtain PVC paste material；It will be above-mentioned
Deaeration under the conditions of 0.09MPa of PVC paste material；PVC paste material is poured into copper mould after deaeration；Above-mentioned copper mould is put into revolution to ward off
Glue stove toasts 5min under conditions of 300 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Use environment-protective water
Property or oiliness toy lacquer to appointed part paint after obtain finished product.
Embodiment 9
Application of the citrate of the present invention in toy, steps are as follows：
100g citrate plasticizers obtained in embodiment 2 and 8g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 95gPVC pastes resin, 5gPVC suspending resins, 5g thinners, 0.8g releasing agents, is uniformly mixing to obtain PVC paste material；It will be above-mentioned
Deaeration under the conditions of 0.09MPa of PVC paste material；PVC paste material is poured into copper mould after deaeration；Above-mentioned copper mould is put into revolution to ward off
Glue stove toasts 5min under conditions of 300 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Use environment-protective water
Property or oiliness toy lacquer to appointed part paint after obtain finished product.
Embodiment 10
Application of the citrate of the present invention in toy, steps are as follows：
It is stirred after 120g citrate plasticizers obtained in embodiment 2 are mixed with 6g epoxidized soybean oils, 3g stabilizers,
100gPVC pastes resin, 5g thinners, 1g releasing agents are put into, PVC paste material is uniformly mixing to obtain；Above-mentioned PVC paste material is existed
Deaeration under the conditions of 0.09MPa；PVC paste material is poured into copper mould after deaeration；Above-mentioned copper mould is put into revolution and wards off glue stove,
5min is toasted under conditions of 300 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Using environment-friendly water-based or oily
Love toys paint obtains finished product after painting to appointed part.
Embodiment 11
Application of the citrate of the present invention in toy, steps are as follows：
70g citrate plasticizers made from the present embodiment 3 are mixed with 8g epoxidized soybean oils, 3g stabilizers, input
80gPVC pastes resin, 20gPVC suspending resins, 8g thinners, 0.6g releasing agents, is uniformly mixing to obtain PVC paste material；By above-mentioned PVC
Thickener deaeration under the conditions of 0.07MPa；PVC paste material is poured into copper mould after deaeration；Above-mentioned copper mould is put into revolution and wards off glue
Stove toasts 6min under conditions of 275 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Using environment-friendly water-based
Or oiliness toy lacquer after appointed part spray painting to obtaining finished product.
Embodiment 12
Application of the citrate of the present invention in toy, steps are as follows：
100g citrate plasticizers obtained, 8g epoxidized soybean oils, 3g stabilizers in embodiment 3 are mixed, thrown
Enter 95gPVC pastes resin, 5gPVC suspending resins, 5g thinners, 0.8g releasing agents, is uniformly mixing to obtain PVC paste material；It will be above-mentioned
Deaeration under the conditions of 0.07MPa of PVC paste material；PVC paste material is poured into copper mould after deaeration；Above-mentioned copper mould is put into revolution to ward off
Glue stove toasts 6min under conditions of 275 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Use environment-protective water
Property or oiliness toy lacquer to appointed part paint after obtain finished product.
Embodiment 13
Application of the citrate of the present invention in toy, steps are as follows：
120g citrate plasticizers obtained in embodiment 3 and 6g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 100gPVC pastes resin, 5g thinners, 1g releasing agents, is uniformly mixing to obtain PVC paste material；By above-mentioned PVC paste material in 0.07MPa
Under the conditions of deaeration；Gained PVC paste material is poured into copper mould after deaeration；Above-mentioned copper mould is put into revolution and wards off glue stove, at 275 DEG C
Under conditions of toast 6min；Recirculated water cooling makes the die sinking of toy product cooling and shaping take out；Use environment-friendly water-based or oiliness toy lacquer
Finished product is obtained after painting to appointed part.
Embodiment 14
Application of the citrate of the present invention in toy, steps are as follows：
70g citrate plasticizers made from the present embodiment 4 are mixed with 8g epoxidized soybean oils, 3g stabilizers, input
80gPVC pastes resin, 20gPVC suspending resins, 8g thinners, 0.6g releasing agents, is uniformly mixing to obtain PVC paste material；By above-mentioned PVC
Thickener deaeration under the conditions of 0.08MPa；Gained PVC paste material after deaeration is poured into copper mould；Above-mentioned copper mould is put into revolution
Glue stove is warded off, 7min is toasted under conditions of 275 DEG C；Recirculated water cooling is molded after so that toy is cooled down product approval and is taken out；Use environmental protection
Aqueous or oiliness toy lacquer obtains finished product after painting to appointed part.
Embodiment 15
Application of the citrate of the present invention in toy, steps are as follows：
100g citrate plasticizers obtained in embodiment 4 and 8g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 95gPVC pastes resin, 5gPVC suspending resins, 5g thinners, 0.8g releasing agents, is uniformly mixing to obtain PVC paste material；By above-mentioned institute
Obtain deaeration under the conditions of 0.08MPa of PVC paste material；Gained PVC paste material after deaeration is poured into copper mould；Above-mentioned copper mould is put again
Enter revolution and ward off glue stove, 7min is toasted under conditions of 275 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Make
Finished product is obtained after being painted to appointed part with environment-friendly water-based or oiliness toy lacquer.
Embodiment 16
Application of the citrate of the present invention in toy, steps are as follows：
120g citrate plasticizers obtained in embodiment 4 and 6g epoxidized soybean oils, 3g stabilizers are mixed, thrown
Enter 100gPVC pastes resin, 5g thinners, 1g releasing agents, is uniformly mixing to obtain PVC paste material；Above-mentioned gained PVC paste material is existed
Deaeration under the conditions of 0.08MPa；Gained PVC paste material after deaeration is poured into copper mould；Above-mentioned copper mould is put into revolution and wards off glue stove,
7min is toasted under conditions of 275 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Using environment-friendly water-based or
Oiliness toy lacquer obtains finished product after painting to appointed part.
4 citrate of table produces the performance of toy
Embodiment 16
Shandong Wan Tu high molecular materials limited liability company is selected to produce tri- kinds of citrate plasticizers of WT1, WT2, WT98
As a comparison case.
The preparation process of the toy is as follows：
100g WT1 citrates, 8g epoxidized soybean oils, 3g stabilizers are mixed, input 95gPVC pastes resin,
5gPVC suspending resins, 5g thinners, 0.8g releasing agents, are uniformly mixing to obtain PVC paste material；Above-mentioned gained PVC paste material is existed
Deaeration under the conditions of 0.06MPa；Gained PVC paste material after deaeration is poured into copper mould；Above-mentioned copper mould is put into revolution and wards off glue stove,
8min is toasted under conditions of 250 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Using environment-friendly water-based or
Oiliness toy lacquer obtains finished product after painting to appointed part.
Embodiment 17
The preparation process of the toy is as follows：
It is stirred after 100g WT2 citrates, 8g epoxidized soybean oils, 3g stabilizers are mixed, input 95gPVC pastes resin,
5gPVC suspending resins, 5g thinners, 0.8g releasing agents, are uniformly mixing to obtain PVC paste material；Above-mentioned gained PVC paste material is existed
Deaeration under the conditions of 0.09MPa；It will be in the copper mould that pours into of gained PVC paste material after deaeration；Above-mentioned copper mould is put into revolution and wards off glue
Stove toasts 5~8min under conditions of 300 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Use environmental protection
Aqueous or oiliness toy lacquer obtains finished product after painting to appointed part.
Embodiment 18
The preparation process of the toy is as follows：
It is stirred after 100g WT98 citrates, 8g epoxidized soybean oils, 3g stabilizers are mixed, input 95gPVC pastes resin,
5gPVC suspending resins, 5g thinners, 0.8g releasing agents, are uniformly mixing to obtain PVC paste material；Above-mentioned gained PVC paste material is existed
Deaeration under the conditions of 0.07MPa；Gained PVC paste material after deaeration is poured into copper mould；
Above-mentioned copper mould is put into revolution and wards off glue stove, 7min is toasted under conditions of 275 DEG C；Recirculated water cooling makes toy produce
It molds and takes out after product cooling and shaping；Finished product is obtained after painting to appointed part using environment-friendly water-based or oiliness toy lacquer.
The performance of table 6WT1, WT2, WT98 production toy
Embodiment 19
Select two kinds of plasticizer of widely used TBC, ATBC as a comparison case.
The preparation process of the toy is as follows：
100g TBC citrates, 8g epoxidized soybean oils, 3g stabilizers are mixed, input 95gPVC pastes resin,
5gPVC suspending resins, 5g thinners, 0.8g releasing agents, are uniformly mixing to obtain PVC paste material；Above-mentioned gained PVC paste material is existed
Deaeration under the conditions of 0.06MPa；Above-mentioned gained PVC paste material is poured into copper mould；Above-mentioned copper mould is put into revolution and wards off glue stove,
5min is toasted under conditions of 250 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Using environment-friendly water-based or oily
Love toys paint obtains finished product after painting to appointed part.
Embodiment 20
The preparation process of the toy is as follows：
100gATBC citrates, 8g epoxidized soybean oils, 3g stabilizers are mixed, input 95gPVC pastes resin,
5gPVC suspending resins, 5g thinners, 0.8g releasing agents, are uniformly mixing to obtain PVC paste material；Above-mentioned gained PVC paste material is existed
Deaeration under the conditions of 0.09MPa；Gained PVC paste material after deaeration is poured into copper mould；Above-mentioned copper mould is put into revolution and wards off glue stove,
5min is toasted under conditions of 300 DEG C；Recirculated water cooling molds taking-up after making toy product cooling and shaping；Using environment-friendly water-based or
Oiliness toy lacquer obtains finished product after painting to appointed part.
The performance of table 8TBC, ATBC production toy
Conclusion：The present invention compared to WT1, WT2, WT98, TBC, ATBC for, toy rear surface of painting is not glutinous, dry and comfortable, no
Be stained with ash, resistance to soiling it is good, in use improve PVC paste material viscosity stability, improve product resistance to migration.
Claims (10)
1. a kind of citrate, characterized in that the citrate at least contains two or more with following molecular formula
1 compound represented of formula：
In formula 1, the group R1、R2And R3For the alkyl of different carbon atom numbers, the group R of the compound1、R2And R3Be C4,
C8 is aliphatic one or two kinds of, group R4For one kind of H or carboxylic acid group.
2. citrate according to claim 1, it is characterised in that in the alkyl, C4 is isobutyl group, and C8 includes just
Octyl and 2- ethylhexyls.
3. citrate according to claim 1, it is characterised in that the citrate average molecular weight be 379.12~
416.53。
4. the preparation method of citrate as described in claim 1, it is characterized in that including the following steps：
A:Esterification：Citric acid, isobutanol, octanol and catalyst are put into reaction kettle of the esterification, agitating and heating, weighs record phase point
From the water generated in device, when water yield reaches theoretical value, then 0.5~1.5h of isothermal reaction is measured by sampling and records acid value,
Cooling discharge is to neutralizing kettle；
B:Alkali cleaning：According to load and acid value, sodium hydroxide solution is configured, maintains temperature between 70~72 DEG C, use is to be neutralized
10%~20% alkali liquid washing of quality of material number is primary, stirs 20~40 minutes, and constant temperature stands 1~1.25h, divides sub-cloud
Waste water；
C:Washing：The temperature in the step (2) is maintained, with 10%~20% softening water washing of material mass number to be washed
Twice, it stirs 20~40 minutes every time, constant temperature stands 1~1.25h, divides sub-cloud waste water；
D:Rectification and purification：The method for taking vacuum distillation, negative pressure maintain -0.095~-0.1Mpa, and temperature is maintained at 138~
140 DEG C, the material after washing in the step (3) is persistently pumped into rectifying column, to remove extra alcohol and fail to divide completely
Water；
E:Decolorization filtering：Material after rectifying in the step (4) is pumped into decoloration kettle, addition waits for decolorization material mass number
0.25%~0.75% activated carbon keeps temperature to stablize between 78~80 DEG C, stirring 20~be pumped into filter after forty minutes
Press filtration is carried out, to obtain purity up to 99.5% or more citrate.
5. the preparation method of citrate according to claim 4, it is characterised in that：In the step A, with citric acid,
Isobutanol and 2-Ethylhexyl Alcohol are reaction raw materials, and the molar ratio of the isobutanol and the 2-Ethylhexyl Alcohol is 1:(0.125
~0.5).
6. application of the citrate as described in claims 1 to 3 in preparing toy, characterized in that use following parts by weight
Several groups are divided into raw material：
7. application of the citrate according to claim 6 in preparing toy, it is characterised in that：The PVC paste resin
The degree of polymerization 1200~1500；The PVC suspending resins degree of polymerization 900~1000；The thinner is 2,2,4- trimethyls 1,3-
The double isobutyrates of pentanediol；The stabilizer is liquid calcium zinc stabilizer；The auxiliary stabilizer is the ring that epoxide number is more than 6.0
Oxygen soybean oil；The releasing agent is methyl-silicone oil.
8. application of the citrate according to claim 6 in preparing toy, it is characterised in that including steps are as follows：
(1) dispensing：It is stirred after the citrate, epoxidized soybean oil, stabilizer are mixed, input PVC paste resin, PVC suspend
Resin, thinner, releasing agent are uniformly mixing to obtain PVC paste material；
(2) deaeration：By PVC paste material deaeration made from the step (1)；
(3) enter mould：PVC paste material made from the step (2) is poured into copper mould；
(4) it heats：It the step (3) copper mould is put into revolution wards off in glue stove and heat；
(5) cooling：Copper after the step (4) is heated has recirculated water cooling, and toy product is made to shape；
(6) it molds：Toy die sinking made from the step (5) is taken out；
(7) it paints：The toy that the step (6) is taken out is made after being painted to appointed part with environment-friendly water-based or oiliness toy lacquer
Finished product.
9. application of the citrate according to claim 8 in preparing toy, it is characterised in that in the step (2),
Deaeration condition is 0.06~0.09MPa.
10. application of the citrate according to claim 8 in preparing toy, it is characterised in that in the step (4)
Heating condition is 250~300 DEG C, 5~8min.
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| CN115337940A (en) * | 2021-05-14 | 2022-11-15 | 江苏理工学院 | Preparation method and application of catalyst for synthesizing triisobutyl citrate |
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