CN1208365C - Method for preparing amino silicone oil modified polyurethane - Google Patents
Method for preparing amino silicone oil modified polyurethane Download PDFInfo
- Publication number
- CN1208365C CN1208365C CN 03126957 CN03126957A CN1208365C CN 1208365 C CN1208365 C CN 1208365C CN 03126957 CN03126957 CN 03126957 CN 03126957 A CN03126957 A CN 03126957A CN 1208365 C CN1208365 C CN 1208365C
- Authority
- CN
- China
- Prior art keywords
- polyethers
- vulcabond
- silicone oil
- silicon oil
- amido silicon
- 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
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 20
- 239000004814 polyurethane Substances 0.000 title claims abstract description 20
- 229920013822 aminosilicone Polymers 0.000 title abstract 6
- 239000003921 oil Substances 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- -1 amido silicon Chemical compound 0.000 claims description 42
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 23
- 238000000077 Auger electron appearance potential spectroscopy Methods 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 8
- 241001112258 Moca Species 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 239000003607 modifier Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920003225 polyurethane elastomer Polymers 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100202428 Neopyropia yezoensis atps gene Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a method for preparing organic silicon modified polyurethane by using amino silicone oil, polyether and diisocyanate as raw materials to generate a copolymerization reaction under the condition of not adding solubilizing agents, which belongs to the technical field of polyurethane. The method comprises the following steps: 1. adding diisocyanate accounting for less than 10% of the mass percentage of polyether to the polyether and then adding the amino silicone oil drop by drop when mixtures are stirred at a high speed at temperature controlled from-5 to 10 DEG C, wherein a mass percentage of the amino silicone oil to the polyether is from 1 to 40%; 2. adding diisocyanate chemically measured after the dropping addition is finished to react for 3 to 6 hours after temperature is raised to 60 to 100 DEG C. The amino silicone oil modified polyurethane material synthesized in the present invention has the advantages of superior mechanical property, favorable surface property and high heat resistance; moreover, the amino silicone oil modified polyurethane material is synthesized under the condition of not adding organic solvents without pollution to environment, and therefore, the present invention conforms to the development direction of green materials.
Description
Technical background the invention belongs to polyurethane field, and relating to a kind of is the novel preparation method of starting material synthesizing organo-silicon-base polyurethane prepolymer for use as with amido silicon oil and vulcabond, polyethers etc.
Technical field urethane (PU) be meant contain in the molecular chain urethano (NHCOO-) and/or isocyanic ester (NCO) high molecular polymer, it is made up of soft chain segment and hard segment, soft chain segment is generally polyethers or polyester, gives polymkeric substance with flexible, toughness.Hard segment be generally aromatic dissocyanate and a micromolecular dibasic alcohol or diamine (as) polycondensate of chainextender, give polymkeric substance with intensity and rigidity.Therefore, polyurethane material generally all has intensity, hardness preferably; Abrasion performance, water-fast, anti-solvent and anti-circumnutating property; Heat stability is good, vibration absorption ability are strong; And performances such as better tissues adaptability and blood compatibility, can be made into multiple product forms such as porous plastics, elastomerics, tackiness agent, coating, be widely used in many fields such as national defence, light industry, traffic, mine, machinery, electronics, building, physical culture.But,, make its application obtain restriction in some fields because that it has is inflammable, not high-low temperature resistant, easy shortcoming such as aging.
Organosilicon (mainly being polysiloxane) has excellent dielectricity, snappiness, lower glass transition temperatures; High-low temperature resistant, resistance to oxidation, UV resistant; The hydrophobicity that low surface energy is become reconciled, ventilation property and biocompatibility; And its performance only has very little change when changing in wide temperature.But its mechanical property, sticking power, wear resistance, solvent resistance is relatively poor, cost is higher.
And organic silicone polyurethane copolymer combines the advantage of above-mentioned two kinds of materials, on the basis of the mechanical property that keeps the polyurethane material excellence, the critical surface tension of polymkeric substance is descended, improve its hydrophobic properties of the surface, improve the consistency of matrix polymer and blood, widened its application widely at aspects such as medical material, coating, tackiness agent.
But because the character of polydimethylsiloxane (PDMS) and urethane (PU) differs greatly, its solubility parameter is respectively 7.5 and 11.3, it is a kind of typical incompatible system, be difficult to reach homogeneous phase and mix, thus solvent generally in the addition polymerization process, often used, to improve both consistencies, at first use α as McGrath, the end capped polydimethylsiloxane of ω-two aminopropyl (ATPS, Mn=4000), use the diamine chain stretching agent chain extension then with vulcabond MDI polycondensation:
The organic silicone polyurethane copolymer of synthetic carries out in solvents tetrahydrofurane.The industrialized Cardiothahe 51 of U.S. Kontron company is synthetic organic silicone polyurethane copolymers that make in the presence of the solvent dioxane, Wang Xiaoping etc. adopt the not substance law synthesizing organo-silicon-polyurethane copolymer of solubilizing agent of the utilization mentioned among the semi-gelled method of solubilizing agent not and the CN1032174A, but the raw material that they utilize is a hydroxy-terminated polysiloxane, the specific activity of itself and di-isocyanate reaction contains a little less than the amino polysiloxane, speed of response is slower, is easy to control.
And has the polysiloxane of active amino modification; because amino is very active; can finish with the moment that is reflected at of isocyanic ester; be easy to take place sudden and violent poly-phenomenon, make reaction to carry out, therefore up to now; all rest on the solvent-borne type stage at the synthetic product by amino-modified silicone urethane in the art; but organic solvent is inflammable and explosive, volatile, smell is big, causes atmospheric pollution during use, has toxicity more or less.Over nearly 10 years, along with the environment pressure from public opinion of preserving our planet grows with each passing day and the enhancing of people's environmental consciousness, the organosilicon-polyurethane material of research and development environment-friendly type is a development trend from now on.
Summary of the invention the purpose of this invention is to provide a kind of synthetic method of urethane of amino-modified silicone, not only have excellent mechanical property, surface property and thermotolerance preferably after this method synthetic material cured, and synthetic method is carried out under the condition that does not add organic solvent, non-environmental-pollution meets the developing direction of " green material ".
The synthetic method of amino-modified silicone urethane provided by the invention is under the condition of solubilizing agent not, uses amido silicon oil, polyethers, vulcabond to be raw material, carries out copolyreaction and makes organic silicon modified polyurethane, comprises the steps:
1, add the mass percent account for polyethers in polyethers and be no more than 10% vulcabond, controlled temperature drips amido silicon oil under-5～10 ℃, high-speed stirring, and wherein the mass percent of amido silicon oil and polyethers is 1～40%;
2, add stoichiometric vulcabond after dropwising, be warming up to 60～100 ℃ of reactions 3～6 hours then.
Wherein amido silicon oil can adopt the molecular weight monoamine with different ammonia values, viscosity, diamine, the polyamines silicone oil between 500～10000, especially the aminoethyl aminopropyl polydimethylsiloxane (as AEAPS) that adopts in the prior art solvent method, amino diamine end-blocking polydimethylsiloxane (as SF930) at main chain.
The mass percent of amido silicon oil and polyethers is 1～40%, preferred 3～20%.
Vulcabond can adopt prior art vulcabond, especially tolylene diisocyanate (TDI), ditan-4 commonly used, 4 '-vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI).
In the whole process of preparation, vulcabond is identical with the consumption and the prior art of polyethers, certain polyethers, and the consumption of vulcabond can pass through stoichiometry.But the mass percent that the control vulcabond accounts for polyethers in the step 1 is no more than 10%, preferred 2～8%.
Polyethers can adopt the prior art polyether glycol of molecular weight between 300～6000 commonly used, as polyoxypropyleneglycol (as N
210, N
220), the polyoxytrimethylene triol is (as N
3010, N
330), polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol, tetrahydrofuran (THF)-propylene oxide copolymerization triol etc., the preferred tetrahydrochysene furan food in one's mouth-propylene oxide copolymerization glycol, tetrahydrofuran (THF)-propylene oxide copolymerization triol.
Temperature of reaction is preferred 70～90 ℃ in the step 2, preferred 3～5 hours of reaction times.
The present invention uses the industrial goods amido silicon oil to make the silicon section, is characterized in, the silicon section is the polysiloxane performed polymer, is not small molecules; Has two or more activity functional groups; And molecule itself contains crosslinkable groups and catalyzing and condensing group, but thereby film formation at low temp; This raw material is industrial goods cheap and easy to get, the amido silicon oil (AEAPS) that the especially present industrial main component of using the most extensively is an aminoethyl aminopropyl polydimethylsiloxane, and its amine value is 0.2～1.2mmol/100g, viscosity is about 1000～5000mpa.s.Next is that industrial goods SF930 main component is the amido silicon oil of the amino-terminated polydimethylsiloxane of line style, and the amine value is 0.2～1.5mmol/100g, and viscosity is 1000～15000mpa.s.
Amino-modified silicone urethane by the present invention's preparation can pass through 3,3 '-two chloro-4,4 '-diamino-ditan (MOCA) composite curing agent and 80wt%2,4-dimethyl sulphide tolylene diamine, 20wt%2,6-dimethyl sulphide tolylene diamine mixture (300
#Solidifying agent) etc. can make the organosilicon-polyurethane elastomer material of excellent property.
The present invention utilizes N
220, N
3010, N
210Have the organosilyl organosilicon-base polyurethane prepolymer for use as of different percentage compositions with the AEAPS synthetic, and obtain elastomer material by solidifying agent curing, its specific performance contrast is as follows:
Table 1 AEAPS, N
220Organosilicon-the urethane and the performance study thereof of preparation
| Sequence number | N 220: AEAPS (mass ratio) | Tensile strength (MPa) | Elongation (%) | Water contact angle (°) | Anti-140 ℃ of 5h mechanical property conservation rates (%) | |
| Tensile strength | Elongation | |||||
| 1 | 100∶0 | 3.68 | 263 | 70 | 47.80 | 57.14 |
| 2 | 100∶6 | 4.01 | 283 | 83 | 49.53 | 71.88 |
| 3 | 100∶10 | 4.81 | 400 | 88 | 60.34 | 73.33 |
| 4 | 100∶0 | 3.15 | 320 | 75 | 35.16 | 48.52 |
| 5 | 100∶15 | 3.48 | 380 | 94 | 52.38 | 60.69 |
Annotate: sequence number 1,2 in the table 1, and 3 is 300
#Solidifying agent solidifies the gained modifier, and sequence number 4,5 is solidified the gained modifier for the MOCA composite curing agent
Table 2 AEAPS, N
3010Preparation organosilicon-urethane and performance study thereof
| Sequence number | N 3010: AEAPS (mass ratio) | Tensile strength (MPa) | Elongation (%) | Water contact angle (°) | Anti-140 ℃ of 5h mechanical property conservation rates (%) | |
| Tensile strength | Elongation | |||||
| 1 | 100∶0 | 3.83 | 236 | 84 | 49.12 | 74.18 |
| 2 | 100∶5 | 4.06 | 220 | 94 | 55.31 | 38.65 |
| 3 | 100∶14 | 4.43 | 175 | 97 | 53.27 | 45.63 |
| 4 | 100∶0 | 3.28 | 280 | 87 | 60.34 | 50.20 |
| 5 | 100∶8 | 3.40 | 254 | 99 | 60.45 | 58.34 |
Annotate: sequence number 1,2 in the table 2, and 3 is 300
#Solidifying agent solidifies the gained modifier, and sequence number 4,5 is solidified the gained modifier for the MOCA composite curing agent
Table 3 AEAPS, N
210Preparation organosilicon-urethane and performance study thereof
| Sequence number | N 210: AEAPS (mass ratio) | Tensile strength (MPa) | Elongation (%) | Water contact angle (°) | Anti-140 ℃ of 5h mechanical property conservation rates (%) | |
| Tensile strength | Elongation | |||||
| 1 | 100∶0 | 8.98 | 250 | 89 | 56.38 | 68.54 |
| 2 | 100∶3 | 8.66 | 265 | 90 | 60.20 | 71.12 |
| 3 | 100∶8 | 8.28 | 287 | 93 | 77.63 | 80.75 |
| 4 | 100∶0 | 4.81 | 300 | 92 | 40.24 | 53.67 |
| 5 | 100∶10 | 4.54 | 335 | 99 | 59.12 | 70.14 |
Annotate: sequence number 1,2 in the table 3, and 3 is 300
#Solidifying agent solidifies the gained modifier, and sequence number 4,5 is solidified the gained modifier for the MOCA composite curing agent
From above-mentioned table 1, table 2, table 3 as can be seen: the organosilicon-urethane cures material through gained behind the amino-modified silicone is compared with unmodified urethane cures material, the physical strength that had both had unmodified urethane excellence, the snappiness (elongation is improved), hydrophobicity (water contact angle increase), the thermotolerance (mechanical property conservation rate height) that have organosilicon again and had prove that the technology that the amido silicon oil that adds has reached expection improves effect.
The present invention is amino amido silicon oil (as the AEAPS) modified polyurethane of side chain except utilizing, and also can utilize amino amido silicon oil (as SF930) at main chain to come modified polyurethane, and obtain modified effect preferably, its mechanical property such as following table:
The different organosilicons of table 4 are to the influence of organosilicon-polyurethane material mechanical property
| Sequence number | Amido silicon oil | N 220: amido silicon oil (mass ratio) | Tensile strength (MPa) | Elongation (%) | Water contact angle (°) | Relative PU0 increment rate (%) | |
| Tensile strength | Elongation | ||||||
| 1 | 100∶0 | 3.68 | 263 | 70±2 | |||
| 2 | AEAPS | 100∶10 | 4.81 | 400 | 86±2 | 30.71 | 52.09 |
| 3 | SF930 | 100∶10 | 3.29 | 306 | 95±2 | -10.59 | 16.35 |
Annotate: table 4 gained material is 300
#Solidifying agent solidifies the gained modifier
As can be seen from the above table: no matter be the amido silicon oil of using side chain, still the amido silicon oil with main chain comes its elongation of modified polyurethane all to be improved, and this is because organosilyl siloxane bond is very soft, can rotate freely, and makes the PU flexibility increase, the elongation raising; Through the organosilicon-polyurethane material 2 after the AEAPS modification, the urethane 1 of relative non-modified, it is because the active group among the AEAPS greater than 2, can form crosslinked that tensile strength improves; And SF930 is amino diamine amido silicon oil at main chain, forms segmented copolymer with urethane and since organosilyl physical strength a little less than, can not form crosslinkedly with urethane again, institute is so that the decline of the tensile strength of material.
The present invention takes the not substance law synthesizing organo-silicon-urethane of solubilizing agent, has the following advantages: 1, copolyreaction does not add organic solvent, does not have environmental pollution; 2, need not organic solvent after reaction finishes handles; 3, the product of the synthetic gained of solvent-borne type even through handling, still have the small amount of residual solvent, pollutes the environment, and institute of the present invention synthetic product, organic solvent-free, the product than the synthetic gained of solvent-borne type has better performance in theory; 4, low temperature, high-speed stirring, the low diisocyanate concentration taked of copolyreaction of the present invention drips conditions such as amido silicon oil, and easy control simple to operate is easy to realize.
The present invention has overcome the shortcoming of existing procucts, remedied the deficiency of prior art, by designing the rational route of a cover, the polyurethane elastomer material that has synthesized amino-modified silicone, make its existing excellent mechanical property, have surface property, thermotolerance preferably again, and should syntheticly be what under the condition that does not add organic solvent, to carry out, non-environmental-pollution meets the developing direction of " green material ".
Preferred forms
Be specific embodiments of the invention below:
Embodiment 1
In the 1000ml container of mechanical electric mixer, thermometer, nitrogen conduit is housed, add N
220(about molecular weight 2000) 500g, TDI 10.7g, under-2 ℃ cold water, mix, under the high-speed stirring condition, drip 15g AEAPS then by dropping funnel, approximately dropwise half an hour, add vulcabond 78.0g, be warmed up to 90 ℃ of reaction 3h then, promptly get modified polyurethane prepolymer, take 300
#Solidifying agent solidifies, and curing process adopts 100 mass parts base polyurethane prepolymer for use as, 7.4 mass parts 300
#Solidifying agent at room temperature mixes fast, is cast in the homemade 8 type matrix tools, through the self-vulcanizing demoulding two days later, curing promptly gets organosilicon-poly-nitrogen ester elastomer material three weeks in the baking oven of 80 ℃ of constant temperature then, and recording tensile strength of material is 3.75MPa, and elongation is 270%.
Embodiment 2
In the 1000ml container of mechanical electric mixer, thermometer, nitrogen conduit is housed, add N
210(about molecular weight 1000) 500g, HDI 28.8g, under 8 ℃ cold water, mix, under the high-speed stirring condition, pass through dropping funnel Dropwise 5 0g AEAPS then, approximately dropwise half an hour, add vulcabond 143.7g, be warmed up to 80 ℃ of reaction 4h then, promptly get modified polyurethane prepolymer, take the MOCA composite curing agent to solidify, curing process adopts 100 mass parts base polyurethane prepolymer for use as, 66.5 mass parts MOCA composite curing agent at room temperature mixes fast, is cast in the homemade 8 type matrix tools, through the self-vulcanizing demoulding two days later, curing promptly got organosilicon-polyurethane elastomer material in three weeks in the baking oven of 80 ℃ of constant temperature then, and recording tensile strength of material is 3.85 MPa, and elongation is 308%.
Embodiment 3
In the 1000ml container of mechanical electric mixer, thermometer, nitrogen conduit is housed, add through pretreated N
3010(about molecular weight 2800) 560g, TDI 25.6g, under 5 ℃ cold water, mix, under the high-speed stirring condition, drip 39.2g AEAPS then by dropping funnel, approximately dropwise half an hour, add vulcabond 83g, be warmed up to then about 78 ℃ of reaction 5h and promptly get modified polyurethane prepolymer, take 300 solidifying agent to solidify, curing process adopts 100 mass parts base polyurethane prepolymer for use as, 7.8 mass parts 300
#Solidifying agent at room temperature mixes fast, is cast in the homemade 8 type matrix tools, through the self-vulcanizing demoulding two days later, curing promptly got organosilicon-polyurethane elastomer material in three weeks in the baking oven of 80 ℃ of constant temperature then, and recording tensile strength of material is 4.18MPa, and elongation is 195%.
Embodiment 4
In the 1000ml container of mechanical electric mixer, thermometer, nitrogen conduit is housed, add through pretreated N
220600g, MDI 45g, under 7 ℃ cold water, mix, under the high-speed stirring condition, drip 90g SF930 then by dropping funnel, approximately dropwise half an hour, add vulcabond 109.6g, be warmed up to then about 85 ℃ of reaction 3.5h and promptly get modified polyurethane prepolymer, take 300
#Solidifying agent solidifies, and curing process adopts 100 mass parts base polyurethane prepolymer for use as, 7.0 mass parts 300
#Solidifying agent at room temperature mixes fast, is cast in the homemade 8 type matrix tools, through the self-vulcanizing demoulding two days later, curing promptly got organosilicon-polyurethane elastomer material in three weeks in the baking oven of 80 ℃ of constant temperature then, and recording tensile strength of material is 3.64MPa, and elongation is 412%.
Embodiment 5
In the 1000ml container of mechanical electric mixer, thermometer, nitrogen conduit is housed, add through pretreated N
220500g, TDI 12g, under 4 ℃ cold water, mix, under the high-speed stirring condition, drip 100g SF930 then by dropping funnel, approximately dropwise half an hour, add vulcabond 78.6g, be warmed up to 83 ℃ of reaction 4h then, promptly get modified polyurethane prepolymer, take the MOCA composite curing agent to solidify, curing process adopts 100 mass parts base polyurethane prepolymer for use as, 35.4 mass parts MOCA composite curing agents, at room temperature mix fast, be cast in the homemade 8 type matrix tools, through the self-vulcanizing demoulding two days later, curing promptly got organosilicon-polyurethane elastomer material in three weeks in the baking oven of 80 ℃ of constant temperature then.Recording tensile strength of material is 2.13MPa, and elongation is 440%.
Claims (9)
1, a kind of synthetic method of amino-modified silicone urethane is under the condition of solubilizing agent not, uses amido silicon oil, polyethers, vulcabond to be raw material, carries out copolyreaction and makes organic silicon modified polyurethane, comprises the steps:
1, add the mass percent account for polyethers in polyethers and be no more than 10% vulcabond, controlled temperature drips amido silicon oil under-5～10 ℃, high-speed stirring, and wherein the mass percent of amido silicon oil and polyethers is 1～40%;
2, add stoichiometric vulcabond after dropwising, be warming up to 60～100 ℃ of reactions 3～6 hours then.
2, the process of claim 1 wherein that amido silicon oil is selected from monoamine with different ammonia values, viscosity, diamine, the polyamines silicone oil of molecular weight between 500～10000.
3, the method for claim 2, wherein amido silicon oil is selected from aminoethyl aminopropyl polydimethylsiloxane, amino diamine end-blocking polydimethylsiloxane at main chain.
4, claim 1 or 2 method, wherein the mass percent of amido silicon oil and polyethers is 3～20%.
5, claim 1 or 2 method, wherein vulcabond is selected from tolylene diisocyanate, ditan-4,4 '-vulcabond, hexamethylene diisocyanate.
6, claim 1 or 2 method, wherein the mass percent that vulcabond accounts for polyethers in the step 1 is 2～8%.
7, claim 1 or 2 method, wherein polyethers is the polyether glycol of molecular weight between 300～6000.
8, the method for claim 7, wherein polyethers is selected from polyoxypropyleneglycol, polyoxytrimethylene triol.
9, claim 1 or 2 method, wherein temperature of reaction is 70～90 ℃ in the step 2, the reaction times is 3～5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03126957 CN1208365C (en) | 2003-06-24 | 2003-06-24 | Method for preparing amino silicone oil modified polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03126957 CN1208365C (en) | 2003-06-24 | 2003-06-24 | Method for preparing amino silicone oil modified polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1470544A CN1470544A (en) | 2004-01-28 |
| CN1208365C true CN1208365C (en) | 2005-06-29 |
Family
ID=34153152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03126957 Expired - Fee Related CN1208365C (en) | 2003-06-24 | 2003-06-24 | Method for preparing amino silicone oil modified polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1208365C (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007028253A1 (en) * | 2007-06-20 | 2008-12-24 | Wacker Chemie Ag | Silicone-containing polyurethane foam |
| CN101220202B (en) * | 2007-08-10 | 2010-08-18 | 上海应用技术学院 | Water-polyurethane/amido organosilicon composite resin |
| CN101891948B (en) * | 2010-07-26 | 2012-07-18 | 山东理工大学 | Preparation method of super hydrophobic polyurethane film with wear resistance property |
| CN102079806B (en) * | 2010-12-15 | 2013-05-15 | 北京航空航天大学 | Preparation and application of a silicone-modified polyurethane elastomer |
| CN102140157A (en) * | 2010-12-23 | 2011-08-03 | 上海凯众聚氨酯有限公司 | Preparation method of high-temperature-resistant MDI (Diphenyl Methane Diisocyanate)-based polyurethane elastomer |
| CN102417595B (en) * | 2011-11-20 | 2013-01-02 | 浙江精业生化有限公司 | Preparation method of novel polyurethane-modified organic silica gel |
| CN103665316B (en) * | 2013-12-09 | 2016-03-02 | 山东一诺威聚氨酯股份有限公司 | The preparation method of organic-silicon-modified MDI |
| CN104211902A (en) * | 2014-08-19 | 2014-12-17 | 深圳高远通新材料科技有限公司 | Preparation method of waterborne polyurethane emulsion and waterborne polyurethane emulsion prepared by preparation method |
| CN104984456B (en) * | 2015-05-25 | 2018-08-28 | 中国科学院长春应用化学研究所 | A kind of antimicrobial form polyurethanes medical instrument, preparation method and Antimicrobial type lien needle peripheral catheters |
| CN105385332A (en) * | 2015-12-25 | 2016-03-09 | 北京展辰新材料有限公司 | Water-based transparent primer and preparation method thereof |
| CN106087451A (en) * | 2016-08-25 | 2016-11-09 | 周荣 | A kind of preparation method of air previous polyurethane artificial leather |
| CN106674481B (en) * | 2016-11-17 | 2019-06-04 | 中国人民解放军61489部队 | A kind of extremely frigid zones concrete works polyurethane foam injecting paste material and method |
| CN107163898A (en) * | 2017-05-19 | 2017-09-15 | 天永诚高分子材料（常州）有限公司 | A kind of preparation method of high temperature resistant type damp solidifying polyurethane PUR |
| CN109666115B (en) * | 2017-10-16 | 2021-09-07 | 万华化学集团股份有限公司 | A kind of aminosilane-terminated modified polyurethane resin and preparation method thereof |
| CN107556483B (en) * | 2017-10-25 | 2020-12-15 | 威海诺葳信和新材料有限公司 | Linear amphoteric carboxyl-terminated polyether amino silicone oil, cross-linked amphoteric carboxyl-terminated polyether amino silicone emulsion softening agent prepared from same and preparation method |
| CN108483979A (en) * | 2018-04-04 | 2018-09-04 | 刘凡领 | A kind of cement waterproof agent |
| CN108976763B (en) * | 2018-05-02 | 2020-03-17 | 歌尔股份有限公司 | Silicone oil modified polyurethane elastomer diaphragm and loudspeaker monomer |
| CN108504321A (en) * | 2018-05-07 | 2018-09-07 | 安吉祥力胶粘剂有限公司 | A kind of organic silicon polyurethane adhesive and preparation method thereof |
| CN109535374B (en) * | 2018-11-28 | 2021-05-11 | 厦门誉匠复合材料有限公司 | Polyurethane elastomer and preparation method thereof |
| CN111040488A (en) * | 2019-12-05 | 2020-04-21 | 曾令涛 | UV hand feeling coating for galvanized plate of household appliance and preparation method thereof |
| CN111690275B (en) * | 2020-07-10 | 2022-03-08 | 清远市宏图助剂有限公司 | Durable-high-adhesion ceramic tile antifouling liquid and using method thereof |
| CN112430310A (en) * | 2020-11-23 | 2021-03-02 | 北京航天新立科技有限公司 | Preparation method of organic silicon modified curing agent for low-surface-energy coating |
| CN114456581B (en) * | 2022-01-24 | 2024-07-19 | 广东安拓普聚合物科技股份有限公司 | Flame-retardant elastic material and preparation method and application thereof |
| CN116153558B (en) * | 2022-09-08 | 2024-12-24 | 北京梦之墨科技有限公司 | High-elastic conductive paste and preparation method and application thereof |
| CN115779129A (en) * | 2022-11-18 | 2023-03-14 | 哈尔滨生材新材料科技发展有限公司 | High-adsorbability porous structure polyurethane dressing |
-
2003
- 2003-06-24 CN CN 03126957 patent/CN1208365C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1470544A (en) | 2004-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1208365C (en) | Method for preparing amino silicone oil modified polyurethane | |
| Sirrine et al. | Urea as a monomer for isocyanate-free synthesis of segmented poly (dimethyl siloxane) polyureas | |
| JP4068968B2 (en) | Silane-terminated polydiorganosiloxane-urethane copolymer | |
| JP3999739B2 (en) | Composition comprising an organopolysiloxane / polyurea / polyurethane block copolymer | |
| JP4221301B2 (en) | Crosslinkable polymer blends containing alkoxysilane-terminated polymers | |
| EP2010588B1 (en) | Organosilicon polyurea polymers, elastomers manufactured therefrom and their use | |
| CN107531872B (en) | Polyurethane | |
| EP2217650B1 (en) | Curable benzoxazine-based compositions, their preparation and cured products thereof | |
| Behera et al. | A novel ionomeric polyurethane elastomer based on ionic liquid as crosslinker | |
| JP7440500B2 (en) | Aspartate functional polysiloxanes, their preparation and their uses | |
| US8748532B2 (en) | Flexible, low temperature, filled composite material compositions, coatings, and methods | |
| CN105793327A (en) | Synthesis and use of metalized polyhedral oligomeric silsequioxane catalyst compositions | |
| CN110054743A (en) | Solvent-free multicomponent system | |
| JP2006521430A (en) | Process for producing organopolysiloxane copolymer and use thereof | |
| KR101313713B1 (en) | compositions of polyurethane resin has anti-hydrolysis property, Manufacturing method of polyurethane resin using the same and polyurethane adhesive with polyurethane resin | |
| CN112210336A (en) | Low-temperature-resistant polyurethane adhesive and preparation method thereof | |
| US20120077950A1 (en) | Compound Suitable as Polymeric Dispersant | |
| Schwab et al. | Polyhedral oligomeric silsesquioxanes (POSS): silicon based monomers and their use in the preparation of hybrid polyurethanes | |
| US8440770B2 (en) | Compositions comprising siloxane copolymers | |
| CN107603551B (en) | Silane modified polyurea and preparation method thereof | |
| CN119775521B (en) | High-strength high-thermoplastic-temperature polysiloxane polyurea thermoplastic elastomer containing dynamic aminal bond and preparation method thereof | |
| JP2003048951A (en) | Blocked polyisocyanate | |
| Shi | Preparation and characterization of poly (trifluoropropylmethyl) siloxane-block-polyurethane-urea elastomers | |
| CN121108452A (en) | Thermoplastic organosilicon polyurethane elastomer and preparation method thereof | |
| CN114456341A (en) | A kind of organosilicon modified polyurethane material and preparation method and application 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 | ||
| ASS | Succession or assignment of patent right |
Owner name: CHINESE ACADEMY OF SCIENCES GUANGZHOU CHEMICALS CO Free format text: FORMER OWNER: GUANGZHOU INST. OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20111028 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20111028 Address after: 510650 Guangdong city of Guangzhou province Tianhe District Xing Branch Road No. 368 Patentee after: Guangzhou Chemistry Co., Ltd. Chinese Academy of Sciences Address before: 510650 Guangdong city of Guangzhou province Tianhe District Wushan happy home Patentee before: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Jinjiang Defu Resin Co., Ltd. Assignor: Guangzhou Chemistry Co., Ltd. Chinese Academy of Sciences Contract record no.: 2012350000003 Denomination of invention: Method for preparing amino silicone oil modified polyurethane Granted publication date: 20050629 License type: Exclusive License Open date: 20040128 Record date: 20120106 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050629 Termination date: 20150624 |
|
| EXPY | Termination of patent right or utility model |