CN1300245C - Thermostable metaformaldehyde containing condensate of melamine and formaldehyde, and its preparation method - Google Patents
Thermostable metaformaldehyde containing condensate of melamine and formaldehyde, and its preparation method Download PDFInfo
- Publication number
- CN1300245C CN1300245C CNB2005100214092A CN200510021409A CN1300245C CN 1300245 C CN1300245 C CN 1300245C CN B2005100214092 A CNB2005100214092 A CN B2005100214092A CN 200510021409 A CN200510021409 A CN 200510021409A CN 1300245 C CN1300245 C CN 1300245C
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- melamine
- condensate
- pom
- thermal stable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims description 21
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 title description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 title 1
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 133
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 122
- -1 polyoxymethylene Polymers 0.000 claims abstract description 48
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019253 formic acid Nutrition 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 195
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 238000010521 absorption reaction Methods 0.000 claims description 35
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- 108010010803 Gelatin Proteins 0.000 claims description 15
- 239000008273 gelatin Substances 0.000 claims description 15
- 229920000159 gelatin Polymers 0.000 claims description 15
- 235000019322 gelatine Nutrition 0.000 claims description 15
- 235000011852 gelatine desserts Nutrition 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000005453 pelletization Methods 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005138 cryopreservation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 6
- JMOVAGHEQHCXLJ-UHFFFAOYSA-N OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O Chemical compound OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O JMOVAGHEQHCXLJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 5
- FJDLQLIRZFKEKJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanamide Chemical compound CC(C)(C)C1=CC(CCC(N)=O)=CC(C(C)(C)C)=C1O FJDLQLIRZFKEKJ-UHFFFAOYSA-N 0.000 claims description 4
- 101001091385 Homo sapiens Kallikrein-6 Proteins 0.000 claims description 4
- 102100034866 Kallikrein-6 Human genes 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229940059574 pentaerithrityl Drugs 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- DLAKLFCULLUIQP-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethanol;propanoic acid Chemical class CCC(O)=O.OCCOCCOCCO DLAKLFCULLUIQP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- CUHVTYCUTYWQOR-UHFFFAOYSA-N formaldehyde Chemical compound O=C.O=C CUHVTYCUTYWQOR-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 abstract 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 13
- 230000032683 aging Effects 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 10
- 230000007774 longterm Effects 0.000 description 9
- 230000006641 stabilisation Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000029087 digestion Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003019 stabilising effect Effects 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- FWVCSXWHVOOTFJ-UHFFFAOYSA-N 1-(2-chloroethylsulfanyl)-2-[2-(2-chloroethylsulfanyl)ethoxy]ethane Chemical compound ClCCSCCOCCSCCCl FWVCSXWHVOOTFJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 150000003140 primary amides Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明公开了一种含三聚氰胺甲醛缩合物(MF)的热稳定性聚甲醛及其制备方法，其特点是(a)将三聚氰胺与甲醛按摩尔比1∶1.2～4加入带有搅拌器、温度计和回流冷凝器的三颈瓶中，于温度60～75℃加入复合分散剂溶液5～15重量份，调节pH＝6.3～6.5，待反应体系出现白色浑浊时，升温至80～95℃反应0.5～1.5小时，调节pH＝6.8～7.2，停止反应，反应物经洗涤、过滤，获得MF缩合物粒径为1～50μm，低温保存、备用；(b)将聚甲醛树脂100重量份、三聚氰胺甲醛缩合物0.07-1.8重量份、抗氧剂0.1-0.5重量份、甲酸吸收剂0.05-0.5重量份、润滑剂0.1-0.5重量份，加入高速混合机内混合均匀，采用排气式双螺杆挤出机熔融混炼，挤出造粒。螺杆转速50-150转/分，料筒温度140-230℃，获得热稳定性聚甲醛材料。
The invention discloses a heat-stable polyoxymethylene containing melamine-formaldehyde condensate (MF) and a preparation method thereof. and the three-necked bottle of the reflux condenser, add 5 to 15 parts by weight of the composite dispersant solution at a temperature of 60 to 75 ° C, adjust the pH = 6.3 to 6.5, and when the reaction system appears white and turbid, raise the temperature to 80 to 95 ° C to react 0.5 ~ 1.5 hours, adjust pH=6.8 ~ 7.2, stop the reaction, the reactant is washed and filtered, and the particle size of the MF condensate obtained is 1 ~ 50 μm, which is stored at low temperature and used for subsequent use; (b) 100 parts by weight of polyoxymethylene resin, melamine formaldehyde Add 0.07-1.8 parts by weight of condensate, 0.1-0.5 parts by weight of antioxidant, 0.05-0.5 parts by weight of formic acid absorbent, and 0.1-0.5 parts by weight of lubricant. Machine melt mixing, extrusion granulation. The rotation speed of the screw is 50-150 rpm, and the temperature of the barrel is 140-230° C. to obtain a thermally stable polyoxymethylene material.
Description
One, technical field
The present invention relates to a kind of thermal stable polyoxymethylene that contains condensate of melamine and formaldehyde (MF) and preparation method thereof, belong to polymer processing field.
Two, background technology
The formaldehyde absorption agent is the very important auxiliary heat stabilizer of polyoxymethylene (POM), the industrial low molecular compounds such as trimeric cyanamide (MA), Dyhard RU 100 that generally adopt are as the formaldehyde absorption agent at present, it is that addition by De Huo Fa H PARA FORMALDEHYDE PRILLS(91,95) on its amido absorbs formaldehyde, owing to contain a large amount of unreacted Huo Fa H atoms on such compound molecule, show higher thermally-stabilised efficient.But remain in production application at following urgent problem: (1) such formaldehyde absorption agent is because molecular weight is low, and is volatile and reduce stabilising effect in the high temperature process process, and condenses and stop up the processing units vaccum exhaust outlet, thereby reduces production efficiency; (2) such formaldehyde absorption agent easily moves the formation mold deposit, has a strong impact on product apparent mass and production efficiency; (3) mechanical property, particularly impelling strength that add affiliation reduction POM body of such formaldehyde absorption agent.People once adopted some macromolecular materials as POM formaldehyde absorption agent.Chinese patent CN1569957A discloses the heat stabilization of polymeric amide to POM, it have Stability Analysis of Structures, molecular weight high and not volatile, with advantages such as the POM consistency is good, but owing to the easy high temperature oxidation variable color of amide group influences the POM apparent mass.Chinese patent ZL96196799.4 has reported and has adopted the vinyl polymer with primary amide base and imide as POM formaldehyde absorption agent, influences its thermostable effect but its high-temperature stability is relatively poor.Chinese patent 94115800.4 has been reported polyformaldehyde composition and uses thereof, this polyformaldehyde composition has adopted condensate of melamine and formaldehyde as the formaldehyde absorption agent, this formaldehyde absorption agent is general condensate of melamine and formaldehyde, its effect is unsatisfactory: the less effect that is difficult to effectively bring into play the formaldehyde absorption agent of consumption, consumption too much can damage the mechanical property of polyoxymethylene.
Three, summary of the invention
The objective of the invention is provides a kind of thermal stable polyoxymethylene that contains condensate of melamine and formaldehyde (MF) and preparation method thereof at the deficiencies in the prior art, be characterized in by the same formaldehyde of MA (FA) condensation polymerization is made its high molecular, improve the thermostability of MA self, thereby improve heat stabilization to POM, reduce mold deposit, improve the POM quality product.
The present inventor finds, MA and formaldehyde (FA) reaction generates condensate of melamine and formaldehyde (MF), the thermostability that improves formaldehyde absorption agent MA is to make it have certain degree of crosslinking and high thermal stability by regulating the MA/FA reactant ratio, keep having on the MA molecule more unreacted Huo Fa H atom simultaneously, have higher thermally-stabilised efficient with the effect of performance formaldehyde absorption agent.On the other hand,, try hard to obtain the little crosslinked MF of suitable particle diameter, form nanometer or micron particle, play the crystallization nucleating agent effect, reduce the problem that diminishes the POM mechanical property because of large usage quantity by to the dispersion agent kind and use quantity research.
Purpose of the present invention is realized that by following technical measures wherein said raw material mark is parts by weight except that specified otherwise.
The formula constituent that contains the thermal stable polyoxymethylene of condensate of melamine and formaldehyde is by weight:
100 parts of molten polyformaldehyde index 9-27g/10min
0.1～0.5 part in oxidation inhibitor
0.07～1.8 part in MF formaldehyde absorption agent
0.05～0.5 part in formic acid absorption agent
0.05～0.5 part of lubricant
Wherein, oxidation inhibitor is four [β-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] pentaerythritol ester, two [3-(the 3-tertiary butyl-5-methyl 4-hydroxy phenyl) propionic acid triethylene Glycol esters, two [3-(3,5-di-t-butyl 4-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester or N, among the N '-hexylidene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide) any.
The formic acid absorption agent is any in magnesium oxide, Calucium Silicate powder, neurosin, magnesium hydroxide, the lime carbonate.
Lubricant is any in Zerol, two hard esteramides, the tetramethylolmethane tristearate.
The preparation method who contains the thermal stable polyoxymethylene of condensate of melamine and formaldehyde:
(1) preparation of condensate of melamine and formaldehyde
Trimeric cyanamide and formaldehyde 1: 1.2 in molar ratio～4 addings are had in the three-necked bottle of agitator, thermometer and reflux exchanger, add 5～15 parts of composite dispersing agents for 60～75 ℃ in temperature, regulate pH=6.3～6.5, when white opacity appears in the question response system, be warming up to 80～95 ℃ of reactions 0.5～1.5 hour, regulate pH=6.8～7.2, stopped reaction, reactant is through washing, filtration, and the particle diameter that obtains condensate of melamine and formaldehyde is 1～50 μ m, cryopreservation, standby.
(2) preparation of thermal stable polyoxymethylene
With 100 parts of polyformaldehyde resins, 0.07～1.8 part of condensate of melamine and formaldehyde, oxidation inhibitor 0.1-0.5 part, formic acid absorption agent 0.05-0.5 part, lubricant 0.1-0.5 part, add in the high-speed mixer and mix, adopt exhaust twin screw extruder melting mixing, extruding pelletization, screw speed 50-150 rev/min, barrel temperature 140-230 ℃, obtain the thermal stable polyoxymethylene material.
The present inventor finds: the mol ratio of MA and FA has considerable influence to the speed of polycondensation and product structure and performance.The relative content of FA is high more in the reaction, and the methylol number of many melamine methylols of generation is just many more, and it is long more that the muddy time appears in system, and polycondensation speed is slow more; Otherwise the methylol number is few more, and unreacted reactive hydrogen atom is many more, and polycondensation speed is then fast more.When the FA too high levels, it is too much to generate the methylol number, in neutrality or slightly acidic reaction medium, mainly carries out etherification reaction, and products therefrom De Huo Fa H is less, then is not suitable for use in the formaldehyde absorption agent.So will select the mol ratio of suitable MA and FA, make MF that certain degree of crosslinking be arranged and stablize, the while keeps unreacted Huo Fa H as much as possible, to bring into play the effect of formaldehyde absorption agent.
Dispersion agent macromolecular chain to growth in polymkeric substance synthetic dispersion medium plays isolation and dissemination, and prevents to generate particle generation cohesion and form gel, and polyvinyl alcohol, carboxylic formaldehyde sodium cellulosate, gelatin are the macromolecule dispersing agents of using always.Polyvinyl alcohol and carboxylic formaldehyde sodium cellulosate dispersion effect are good, but guarantor's glue power is poor, and particle becomes big during typing, is prone to adhesion.Use gelatin separately, dispersion effect is undesirable, but it is strong to protect glue power, and not have obvious change big for particle during typing, adhesion phenomenon do not occur.Therefore, make dispersion agent, make it have dispersive ability and guarantor's glue power preferably concurrently at appropriate to the occasion gelatin/carboxylic formaldehyde sodium cellulosate sodium or the gelatin/polyvinyl alcohol mixture selected for use of preparation MF condenses.Suitable dispersant dosage can obtain the polymer beads of appropriate particle size size.
Composite dispersing agent is gelatin/carboxylic formaldehyde sodium cellulosate, gelatin/polyvinyl alcohol, and wherein the part by weight of gelatin and carboxylic formaldehyde sodium cellulosate or polyvinyl alcohol is 4: 1～2.5.
Oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol esters, it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester or N, any among the N '-hexylidene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide).
The formic acid absorption agent is any in magnesium oxide, Calucium Silicate powder, neurosin, magnesium hydroxide or the lime carbonate.
Lubricant is any in Zerol, two hard esteramides, the tetramethylolmethane tristearate.
The thermal stable polyoxymethylene performance
In the POM extrusion process, for the POM that is added with low molecule formaldehyde absorption agents such as trimeric cyanamide, Dyhard RU 100, find that at the forcing machine vaccum exhaust outlet adularescent material occurs, and increase gradually, may be such low molecular heat stablizer at high temperature volatilize condense due to; The POM that is added with MF does not then have this phenomenon at venting port, efficiently solves the medium-term and long-term vaccum exhaust outlet blockage problem that exists of POM industrial production.
1, in the POM/MF system with the sample of different MF content in 220 ℃ of isothermals its thermal weight loss rate of survey after weightless 1 hour.After adding formaldehyde absorption agent MF, the more blank POM of thermal weight loss rate of system (MF content is zero) has obvious decline.Increase with the MF consumption, POM thermal weight loss rate sharply descends, when the MF consumption surpasses 0.7wt%, the thermal weight loss rate of POM descends comparatively slow, when the MF consumption reaches 1wt%, the thermal weight loss rate of POM system descends 35% than blank system, as shown in Figure 1, shows that MF has good heat stabilization to POM.
2, the POM system is surveyed the logarithm of its residual mass percentage (R) and the relation of heat-up time 222 ℃ of isothermal weightlessness.The POM thermal weight loss rate that is added with 0.1wt%MA or 1wt%MF descends in time and does not obviously add the slow of formaldehyde absorption agent, the POM thermal weight loss fall off rate that is added with MA is with being added with the close of MF, as shown in Figure 2, show that 1wt%MF is suitable to thermally-stabilised efficient and the 0.1wt%MA of POM.
3, the balancing torque of POM descends with the mixing time increase.To not adding the POM of formaldehyde absorption agent, balancing torque is lower, and having to go to the toilet at the 30min of test falls sharply to 1.5Nm.Adding formaldehyde absorption agent can significantly improve the balancing torque of POM, to being added with the POM of MF, its balancing torque fall off rate is starkly lower than the POM that is added with MA, its balancing torque value is respectively 1.9Nm and 1.6Nm in the 30min of test, show that in the POM course of processing MF has higher thermally-stabilised efficient than MA to POM.
4, the Thermal Decomposition Characteristics temperature that contains the POM system of MF comprises thermolysis starting temperature (T
Onset), the temperature (T of maximum weight loss rate correspondence
Peak) and thermolysis final temperature (T
End)
dHeat decomposition temperature T with weightless 5%, 10%, 20%, 50% correspondence
5%, T
10%, T
20%, T
50%, close with the POM system that contains MA, and their maximum weight loss rate V
MaxAlso close, be respectively 3.4%/℃ and 3.7%/℃, as shown in table 1, show that MF is suitable to heat stabilization and the MA of POM.
5, the POM sample is extruded 5 times through twin screw extruder, test is yellowness index (YI), melting index (MI) and the mechanical property of each time material relatively.Fig. 3 and 4 expressions contain the YI of many extruded materials of POM of MA and MF and the MI variation relation with the processing number of times.As can be seen, increase with the processing number of times, the YI increase degree that is added with the POM of MF is lower than the POM that is added with MA.The initial MI of the two is close, and with the increase of processing number of times, the MI that is added with the POM of MF is lower than the POM that is added with MA.Extrude processing through 5 times, the YI that is added with the POM of MF and MA increases percentage and is respectively 34.5% and 50.5%, and MI increases percentage and is respectively 15.5% and 27.3%.Show that adopting MF to replace MA can make POM slow down molecular weight reduction degree and yellowing in the high-temperature fusion course of processing as the formaldehyde absorption agent, has better heat stabilization with respect to MA.The weight-average molecular weight that calculates the POM of different processing number of times is listed in table 2.Fig. 5～7 are the POM/MA that repeatedly extrudes and the mechanical property of POM/MF sample.The tensile strength of the two changes little in five processing.The notched Izod impact strength of POM/MA sample and elongation at break increase with the processing number of times and descend, and illustrate that degraded has taken place the POM work in-process, molecular weight and molecular weight, thus cause particularly impelling strength reduction of mechanical property.Increase with the processing number of times, the elongation at break and the notched Izod impact strength of POM/MF sample all increase, and this may be that the MF volatility is low, are repeatedly still keeping the heat stabilization higher to POM in the processing, thereby are effectively slowing down POM molecular degradation and molecular weight and molecular weight; On the other hand, the consistency between MF and the POM repeatedly also is being improved in the processing.
6, the POM sample behind the aging certain hour, is tested relatively YI, MI and the mechanical property of each time material in 140 ℃ of Electric heat ovens.Fig. 8 and 9 expressions contain the YI of POM of MA and MF and the MI variation relation with digestion time.The initial YI that is added with the POM of MF is higher than the POM that is added with MA, but with the increase of digestion time, its YI increase degree is lower than the POM that is added with MA; The initial MI of the two is close, and with the increase of digestion time, the MI that is added with the POM of MF increases degree and also is lower than the POM that is added with MA.Through thermo-oxidative ageing 15 days, the YI that is added with the POM of MF and MA increased percentage and is respectively 57.5% and 76.4%, and MI increases percentage and is respectively 20.1% and 27.2%.Show that MF can effectively slow down POM molecular weight in long term thermal oxygen aging process and reduce and yellowing.The weight-average molecular weight that calculates the POM of different digestion times is listed in table 3.The mechanical property of Figure 10～12 expression thermo-oxidative ageing sample POM/MA and POM/MF.The tensile strength of the two, elongation at break and notched Izod impact strength all increase in the time of three days in thermal ageing, and this may be under comparatively high temps, because the thermal induction crystallization causes due to the sample crystallization improves more.Increase with thermal aging time, the tensile strength of the two changes little, and elongation at break descends to some extent.The notched Izod impact strength of POM/MA sample increases with digestion time and reduces, and this may be because degraded takes place under hot oxygen effect POM causes due to the molecular weight reduction; The notched Izod impact strength of POM/MF sample does not have obvious decline.
The present invention has following advantage:
The present invention is directed in the present POM industrial production low molecular compound formaldehyde absorption agents such as the trimeric cyanamide (MA) that generally adopts, Dyhard RU 100 have volatile forfeiture and reduce stabilising effect and condense stop up the processing units vaccum exhaust outlet and reduce production efficiency, easily migration forms mold deposit, reduces problems such as POM body mechanical property, by MA is made its high molecular with the FA condensation polymerization, improve the thermostability of MA self, thereby improve heat stabilization POM.Obtain to have suitable degree of crosslinking and high thermal stability MF condenses by regulating the MA/FA reaction ratio, on the MF molecule, keep unreacted Huo Fa H simultaneously as much as possible, have higher thermally-stabilised efficient with the effect of performance formaldehyde absorption agent; By research to dispersion agent kind, consumption, regulate control MF condenses particle diameter, form nanometer or micron particle, make it have certain crystallization nucleation effect to POM, effectively improve the mechanical property, particularly impelling strength that makes POM.By to the research of MF condenses synthetic technology, obtained to have certain degree of crosslinking, Stability Analysis of Structures, thermally-stabilised efficient is higher and particle diameter is less MF, be characterized in:
1, the MF molecular weight height of the present invention's preparation, volatility is low, can not volatilize and obstruction forcing machine vaccum exhaust outlet in the processing of POM high-temperature fusion, efficiently solves the medium-term and long-term vaccum exhaust outlet blockage problem that exists of POM suitability for industrialized production.
2, the MF of the present invention's preparation has suitable MA/FA mol ratio, make MF that certain degree of crosslinking be arranged and stablize, keep simultaneously unreacted Huo Fa H as much as possible, effect with performance formaldehyde absorption agent, has higher thermally-stabilised efficient, can produce thermostabilization preferably to polyoxymethylene, reach higher thermostabilization effect.
3, the MF of the present invention preparation is difficult for migration formation mold deposit with the polyoxymethylene consistency is good, good dispersity.
4, the MF particle diameter of the present invention preparation is 1～50 μ m, forms nanometer or micron particle and keeps polyoxymethylene mechanical property preferably.
Four, description of drawings
Fig. 1 MF consumption influences POM thermal weight loss rate
Fig. 2 contains the POM isothermal degradation rate curve of different formaldehyde absorption agents
The YI value of many processing of Fig. 3 POM
The MI value of many processing of Fig. 4 POM
The tensile strength of many processing of Fig. 5 POM
The elongation at break of many processing of Fig. 6 POM
The simply supported beam notched Izod impact strength of many processing of Fig. 7 POM
The MI value of Fig. 8 POM long-term aging
The YI value of Fig. 9 POM long-term aging
The tensile strength of Figure 10 POM long-term aging
The elongation at break of Figure 11 POM long-term aging
The simply supported beam notched Izod impact strength of Figure 12 POM long-term aging
Four, embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
100g MA is added in the three-necked bottle, press MA and FA mol ratio and add formaldehyde solution at 1: 1.2.Be warming up to 60 ℃, add 5g gelatin/carboxylic formaldehyde sodium cellulosate (4: 1) composite dispersing agent, adjust pH to 6.3 after white opacity appears in the question response system, is warming up to 95 ℃, reacts adjust pH to 7.0, termination reaction 1 hour.Condensation product is cryopreservation after washing, filtration.
With polyformaldehyde resin 10Kg and four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 50g, carbamide condenses 70g, lime carbonate 20g, Zerol 10g add in the high-speed mixer and mix, adopt exhaust twin screw extruder melting mixing, extruding pelletization obtains thermal stable polyoxymethylene.Screw speed, 50 rev/mins; Barrel temperature, 140-190 ℃.
100gMA is added in the there-necked flask, press MA and FA mol ratio and add formaldehyde solution at 1: 1.5, heating in water bath also stirs.Be heated to 75 ℃, add 10g gelatin/carboxylic formaldehyde sodium cellulosate (4: 1.5) composite dispersing agent, adjust pH to 6.5 after white opacity appears in the question response system, is warming up to 90 ℃, reacts adjust pH to 7.2, termination reaction 1.5 hours.Condensation product is cryopreservation after washing, filtration.
[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol ester 40g, carbamide condenses 90g, magnesium oxide 10g, two hard esteramides 20g add in the high-speed mixer and mix with polyformaldehyde resin 10Kg and two, adopt exhaust twin screw extruder melting mixing, extruding pelletization obtains thermal stable polyoxymethylene.Screw speed, 90 rev/mins; Barrel temperature, 150-200 ℃.
100gMA is added in the there-necked flask, press MA and FA mol ratio and add formaldehyde solution at 1: 2, heating in water bath also stirs.Be heated to 70 ℃, add 15g gelatin/polyvinyl alcohol (4: 2) composite dispersing agent, adjust pH to 6.4 after white opacity appears in the question response system, is warming up to 93 ℃, reacts adjust pH to 6.8, termination reaction 1 hour.Condensation product is cryopreservation after washing, filtration.
With polyformaldehyde resin 10Kg with two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester 30g, carbamide condenses 150g, Calucium Silicate powder 7g, tetramethylolmethane tristearate 10g add in the high-speed mixer and mix, adopt exhaust twin screw extruder melting mixing, extruding pelletization obtains thermal stable polyoxymethylene.Screw speed, 150 rev/mins; Barrel temperature, 170-230 ℃.
100gMA is added in the there-necked flask, press MA and FA mol ratio and add formaldehyde solution at 1: 3, heating in water bath also stirs.Be heated to 70 ℃, add 15g gelatin/polyvinyl alcohol (4: 2.5) composite dispersing agent, adjust pH to 6.3 after white opacity appears in the question response system, is warming up to 95 ℃, reacts adjust pH to 7.0, termination reaction 0.5 hour.Condensation product is cryopreservation after washing, filtration.
With polyformaldehyde resin 10Kg and N, N '-hexylidene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide) 50g, carbamide condenses 180g, neurosin 10g, two hard esteramides 30g add in the high-speed mixer and mix, adopt exhaust twin screw extruder melting mixing, extruding pelletization obtains thermal stable polyoxymethylene.Screw speed, 90 rev/mins; Barrel temperature, 170-230 ℃.
100gMA is added in the there-necked flask, press MA and FA mol ratio and add formaldehyde solution at 1: 4, heating in water bath also stirs.Be heated to 65 ℃, add 5g gelatin/carboxylic formaldehyde sodium cellulosate (4: 1) composite dispersing agent, adjust pH to 6.5 after white opacity appears in the question response system, is warming up to 90 ℃, reacts adjust pH to 7.1, termination reaction 1.5 hours.Condensation product is cryopreservation after washing, filtration.
With polyformaldehyde resin 10Kg with two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester 30g, carbamide condenses 100g, magnesium hydroxide 7g, tetramethylolmethane tristearate 20g add in the high-speed mixer and mix, adopt exhaust twin screw extruder melting mixing, extruding pelletization obtains thermal stable polyoxymethylene.Screw speed, 120 rev/mins; Barrel temperature, 140-220 ℃.
Comparison example:
[3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol ester 50g, trimeric cyanamide 10g, lime carbonate 20g, Zerol 10g add in the high-speed mixer and mix with polyformaldehyde resin 10Kg and two, adopt exhaust twin screw extruder melting mixing, extruding pelletization obtains thermal stable polyoxymethylene.Screw speed, 50 rev/mins; Barrel temperature, 180-220 ℃.
Table 1 contains the POM TGA temperature (air) of different formaldehyde absorption agents
| The formaldehyde absorption agent | T onset (℃) | T peak (℃) | T end (℃) | V max (％/℃) | T 5％ (℃) | T 10％ (℃) | T 20％ (℃) | T 50％ (℃) |
| MA MF | 309.9 310.4 | 326 325.5 | 338.1 334.5 | 3.7 3.4 | 294.3 294.2 | 302.8 303.7 | 311.8 311.7 | 323.4 323.6 |
Weight-average molecular weight (the M of many processing of table 2POM
w)
| The processing number of times | M w | |
| POM/MA | POM/MF | |
| 1 2 3 4 5 | 67127 65811 63808 62564 61372 | 67426 66474 65564 65292 64306 |
Weight-average molecular weight (the M of table 3POM long-term aging
w)
| Digestion time (my god) | M w | |
| POM/MA | POM/MF | |
| 0 3 7 15 | 67127 66162 64482 61376 | 67426 66887 64712 63296 |
Claims (5)
1, the preparation method who contains the thermal stable polyoxymethylene of condensate of melamine and formaldehyde is characterized in that the formula constituent of this thermal stable polyoxymethylene is by weight:
100 parts of molten polyformaldehyde index 9-27g/10min
0.07～1.8 part in condensate of melamine and formaldehyde formaldehyde absorption agent
0.1～0.5 part in oxidation inhibitor
0.05～0.5 part in formic acid absorption agent
0.1～0.5 part of lubricant
This thermal stable polyoxymethylene prepares as follows:
(1) preparation of condensate of melamine and formaldehyde
Trimeric cyanamide and formaldehyde 1: 1.2 in molar ratio～4 addings are had in the three-necked bottle of agitator, thermometer and reflux exchanger, add 5～15 parts of composite dispersing agents for 60～75 ℃ in temperature, regulate pH=6.3～6.5, when white opacity appears in the question response system, be warming up to 80～95 ℃ of reactions 0.5～1.5 hour, regulate pH=6.8～7.2, stopped reaction, reactant is through washing, filtration, and the particle diameter that obtains condensate of melamine and formaldehyde is 1～50 μ m, cryopreservation, standby;
(2) preparation of thermal stable polyoxymethylene material
With 100 parts of polyformaldehyde resins, condensate of melamine and formaldehyde 0.07-1.8 part, oxidation inhibitor 0.1-0.5 part, formic acid absorption agent 0.05-0.5 part, lubricant 0.1-0.5 part, add in the high-speed mixer and mix, adopt exhaust twin screw extruder melting mixing, extruding pelletization, screw speed 50-150 rev/min, barrel temperature 140-230 ℃, obtain thermal stable polyoxymethylene.
2, according to the described preparation method who contains the thermal stable polyoxymethylene of condensate of melamine and formaldehyde of claim 1, it is characterized in that composite dispersing agent is gelatin/carboxylic formaldehyde sodium cellulosate, gelatin/polyvinyl alcohol, wherein the part by weight of gelatin and carboxylic formaldehyde sodium cellulosate or polyvinyl alcohol is 4: 1～2.5.
3, according to the described preparation method who contains the thermal stable polyoxymethylene of condensate of melamine and formaldehyde of claim 1, it is characterized in that oxidation inhibitor is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic acid triethylene Glycol esters, two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] 1,6-hexylene glycol ester or N, among the N '-hexylidene two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide) any.
4,, it is characterized in that the formic acid absorption agent is any in magnesium oxide, Calucium Silicate powder, neurosin, magnesium hydroxide or the lime carbonate according to the described preparation method who contains the thermal stable polyoxymethylene of condensate of melamine and formaldehyde of claim 1.
5,, it is characterized in that lubricant is any in Zerol, two hard esteramides, the tetramethylolmethane tristearate according to the described preparation method who contains the thermal stable polyoxymethylene of condensate of melamine and formaldehyde of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100214092A CN1300245C (en) | 2005-08-04 | 2005-08-04 | Thermostable metaformaldehyde containing condensate of melamine and formaldehyde, and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100214092A CN1300245C (en) | 2005-08-04 | 2005-08-04 | Thermostable metaformaldehyde containing condensate of melamine and formaldehyde, and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1730545A CN1730545A (en) | 2006-02-08 |
| CN1300245C true CN1300245C (en) | 2007-02-14 |
Family
ID=35962969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100214092A Expired - Fee Related CN1300245C (en) | 2005-08-04 | 2005-08-04 | Thermostable metaformaldehyde containing condensate of melamine and formaldehyde, and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1300245C (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341940C (en) * | 2006-03-08 | 2007-10-10 | 四川大学 | Prepn of polyformaldehyde material with polyurethane-base composite fire retardant |
| CN100365061C (en) * | 2006-05-24 | 2008-01-30 | 云南云天化股份有限公司 | Polyformaldehyde amine treatment heat stabilization method |
| CN101508819B (en) * | 2009-03-18 | 2011-08-31 | 四川大学 | Thermal stable polyoxymethylene containing high-efficiency anti-oxidant and method for producing the same |
| CN103160061B (en) * | 2011-12-09 | 2015-09-30 | 金发科技股份有限公司 | There are copolymerized methanal composition and the preparation and application of thermostability and colour stability |
| CN104212119B (en) * | 2013-05-30 | 2018-04-27 | 上海杰事杰新材料(集团)股份有限公司 | A kind of heat-proof water polyformaldehyde composition and preparation method thereof |
| CN103483763B (en) * | 2013-09-05 | 2018-04-17 | 安徽科聚新材料有限公司 | A kind of POM composite materials and preparation method thereof |
| CN106243611A (en) * | 2016-08-31 | 2016-12-21 | 江苏互胜新材料科技有限公司 | Polyformaldehyde high stable basis master batch and preparation method thereof |
| WO2018204809A1 (en) | 2017-05-05 | 2018-11-08 | Ticona Llc | Polyoxymethylene polymer composition that is chemical resistant |
| CN107325475A (en) * | 2017-08-24 | 2017-11-07 | 柳州市日海汽配有限责任公司 | High-intensity plastic product |
| CN109082069A (en) * | 2018-09-21 | 2018-12-25 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of thermal oxidation stability type polyformaldehyde |
| CN114685933B (en) * | 2021-12-15 | 2024-01-02 | 江苏金发科技新材料有限公司 | Polyformaldehyde composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103414A (en) * | 1993-08-24 | 1995-06-07 | 泛塑料株式会社 | Polyoxymethylene composition and molded article thereof |
| CN1196073A (en) * | 1995-09-07 | 1998-10-14 | 旭化成工业株式会社 | Polyoxymethylene resin composition |
| CN1569957A (en) * | 2004-04-27 | 2005-01-26 | 四川大学 | Thermal stability metaformaldehyde and its preparation method |
-
2005
- 2005-08-04 CN CNB2005100214092A patent/CN1300245C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103414A (en) * | 1993-08-24 | 1995-06-07 | 泛塑料株式会社 | Polyoxymethylene composition and molded article thereof |
| CN1196073A (en) * | 1995-09-07 | 1998-10-14 | 旭化成工业株式会社 | Polyoxymethylene resin composition |
| CN1569957A (en) * | 2004-04-27 | 2005-01-26 | 四川大学 | Thermal stability metaformaldehyde and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1730545A (en) | 2006-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1300245C (en) | Thermostable metaformaldehyde containing condensate of melamine and formaldehyde, and its preparation method | |
| CN109825045B (en) | A kind of graphene composite biomass reinforced PBS/PBAT biodegradable composite material and preparation method thereof | |
| CN110372941B (en) | High-density polyethylene pipe and preparation method thereof | |
| CN109181297B (en) | High-fluidity bio-based polyamide 56 resin composition and preparation method thereof | |
| CN109852044A (en) | Thermally conductive nylon of a kind of boron nitride orientation and preparation method thereof | |
| CN110483961A (en) | A kind of degradable mulch and preparation method thereof | |
| CN113003563A (en) | Modified lignin carbon dots and preparation method and application thereof | |
| CN103450628B (en) | A kind of polyacetal resin composite and preparation method thereof | |
| CN116804086B (en) | Long-chain alkyl-polar group co-modified polysiloxane and preparation method thereof | |
| CN1256381C (en) | Thermal stability metaformaldehyde and its preparation method | |
| CN1136323A (en) | Formaldehyde copolymer resin composition | |
| CN103044852A (en) | Polyacetal resin composition | |
| CN118755230B (en) | Flame-retardant phenolic moulding compound and preparation method thereof | |
| CN1765976A (en) | A kind of polypropylene foam premix and preparation method thereof | |
| CN101735509A (en) | Micron-nano silicon carbide/polypropylene composite and preparation method thereof | |
| CN1292808A (en) | Expandable polyvinyl chloride resin composition | |
| CN102786788A (en) | Degradable poly-methyl ethylene carbonate base composite material and preparation method thereof | |
| CN102086285A (en) | Eggshell filler having high beta nucleation on polypropylene and preparation method thereof | |
| CN107163454A (en) | The PVC and preparation method of a kind of heat oxygen aging resistance | |
| CN1664004A (en) | Polyester/unidimensional nano silicate composite materials and method for preparing same | |
| CN1891753A (en) | Polyformamine treatment thermal stabilizing method | |
| CN102268197A (en) | Preparation method of modified filling material with high beta-nucleation effect on polypropylene and preparation method of beta-crystal polypropylene or copolymer of the beta-crystal polypropylene | |
| CN1034417C (en) | Urea-formaldehyde resin for middle density fibre board use and preparing process | |
| CN113621192A (en) | Preparation process of cold-resistant heat-resistant modified plastic particles | |
| CN1032352A (en) | White emulsion binder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070214 Termination date: 20130804 |