CN100500762C - Pouring type urethane elastomer composition - Google Patents
Pouring type urethane elastomer composition Download PDFInfo
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- CN100500762C CN100500762C CNB2007101138803A CN200710113880A CN100500762C CN 100500762 C CN100500762 C CN 100500762C CN B2007101138803 A CNB2007101138803 A CN B2007101138803A CN 200710113880 A CN200710113880 A CN 200710113880A CN 100500762 C CN100500762 C CN 100500762C
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Abstract
The cast polyurethane elastomer composition is one double component system, which consists either of one pre-polymer component obtained through reacting MDI/TDI diisocyanate and polyether at 70-90 deg.c and with isocyanate radical content in 4-6 % and one aromatic binary amine curing agent component; or of one pre-polymer component obtained through reacting diisocyanate and polyether at 70-90 deg.c and with isocyanate radical content in 8-14 % and one polymer component prepared with polypropylene oxide ether polyol, aromatic binary amine curing agent and catalyst. The cast polyurethane elastomer composition has low free TDI content in the pre-polymer, excellent processing performance from the chain expanding agent aromatic amine, and capacity of producing products with excellent mechanical performance.
Description
Technical field
The present invention relates to a kind of pouring type urethane elastomer composition.
Background technology
Urethane is the high molecular synthetic material of a kind of performance between rubber and plastics, is characterized in that the hardness setting range is wide, and the elasticity of existing rubber has the hardness of plastics again, has favorable mechanical performance, wear resisting property and rebound performance.The prepolymer that is used to produce polyurethane elastomer all adopts TDI or MDI and polyol reaction to make usually, the former adopts amine chain extender to be used for the production of polyurethane elastomer usually, as MOCA, DMTDA etc., the latter adopts the alcohols chainextender as 1,4 butyleneglycol, HQEE etc. usually.Because the saturation steam of TDI forces down, the volatility height, toxicity is big, and TDI type polyurethane prepolymer can cause bigger harm to human body in the production and the course of processing.And the saturated vapor pressure height of MDI is not volatile, and is less to the harm of human body, but that MDI type polyurethane prepolymer uses speed of response is fast, and process industrial art performance is poor.
Summary of the invention
It is little that technical problem to be solved by this invention provides a kind of toxicity, can make goods have the pouring type urethane elastomer composition of excellent mechanical property.
The pouring type urethane elastomer composition that solves the problems of the technologies described above, the present invention adopts bicomponent system, and dual mode is arranged respectively.
First kind: comprise A component and B component
A component: a kind of prepolymer, obtain according to the method for being prepared as follows: by weight percentage, reacted 2～3 hours at 70 ℃～90 ℃ by vulcabond 25%～35% and polyether glycol 65%～75%, obtain isocyano-content and be 4～6% prepolymer, it is 2 or 3 that described polyether glycol adopts functionality, the poly(propylene oxide) ethoxylated polyhydric alcohol (PPG) of number-average molecular weight in 1000～3000 scopes, described vulcabond is made up of diphenylmethanediisocyanate and tolylene diisocyanate (TDI) blend, wherein tolylene diisocyanate accounts for 5%～50%, preferred 5%～20% of blend vulcabond gross weight.
The B component: a kind of aromatic diamine solidifying agent, be selected from 3,3 '-dichloro-4,4 '-diaminodiphenyl-methane (MOCA) or 3,5-diformazan sulfenyl tolylene diamine (DMTDA), preferred MOCA.
A component and B component are packed separately, when being used for production of articles, with diamine curing agent (B component) and prepolymer (A component) with 0.85～1.0NH
2The equivalence ratio of/NCO is carried out hybrid reaction, and mixing temperature is 75 ℃～90 ℃.Then according to common mode pour into a mould, sulfidization molding, the goods curing temperature is 100 ℃～115 ℃, vulcanizes the demoulding in 20～60 minutes, 100 ℃～115 ℃ postcure 8～10 hours, obtains the polyurethane elastomer goods.
Second kind:
C component: a kind of prepolymer, obtain according to the method for being prepared as follows: by weight percentage, reacted 2～3 hours at 70 ℃～90 ℃ by vulcabond 30%～50% and polyether glycol 50%～70%, obtain isocyano-content and be 8～14% prepolymer, it is 2 or 3 that described polyether glycol adopts functionality, the poly(propylene oxide) ethoxylated polyhydric alcohol of number-average molecular weight in 1000～3000 scopes, described vulcabond is made up of diphenylmethanediisocyanate and tolylene diisocyanate (TDI) blend, wherein tolylene diisocyanate accounts for 5%～50%, preferred 5%～20% of blend vulcabond gross weight.
D component: a kind of polymeric constituent, obtain according to the method for being prepared as follows: by weight percentage, with functionality is 2 or 3, the poly(propylene oxide) ethoxylated polyhydric alcohol 69.5%～81% of molecular weight in 1000～3000 scopes, aromatic diamine solidifying agent 18%～30%, catalyzer 0.2%～1%, at 100～110 ℃, dewater below-the 0.095MPa to moisture less than 0.05%, obtain polymeric constituent, wherein catalyzer is selected from dibutyl tin laurate, organic lead, organo-bismuth, organic zinc, in the organic mercury one or more, the aromatic diamine solidifying agent is selected from 3,3 '-dichloro-4,4 '-diaminodiphenyl-methane or 3,5-diformazan sulfenyl tolylene diamine.
C component and D component are packed separately, when being used for production of articles, prepolymer mixes with the part by weight of polymeric constituent with 1:1, mixing temperature is 25 ℃～40 ℃, then according to common mode pour into a mould, sulfidization molding, the goods curing temperature is 70 ℃～100 ℃, vulcanizes 20 minutes, obtains the polyurethane elastomer goods.
Appellation A, B, C, D component are just for the convenience on explaining.
Wherein the polyether glycol in A or C prepolymer and the D component can specifically be selected PPG2000, PPG3000, PPG1000, PPG3600 etc. for use.Described diphenylmethanediisocyanate can be the diphenylmethanediisocyanate (liquefied mdi) of pure diphenylmethanediisocyanate (MDI-100), the modification of charing diimine, contains 50%2, the MDI-50 of 4-MDI.
The present invention adopts MDI/TDI blend vulcabond to be used for the synthetic of prepolymer, owing to mainly adopted vulcabond based on MDI, greatly reduce the content of free TDI in the prepolymer, reduced in the production process TDI to the injury of human body, select for use arylamine class chainextender to be used for the making of polyurethane elastomer, processing performance is good, and goods have excellent mechanical property.Be mainly used in the making of polyether(poly)urethane elastomeric article, as goods such as urethane rubber tire, polyurethane plate, rubber rolls.
Embodiment
The embodiment material therefor is as follows:
PPG2000 number-average molecular weight 20000, degree of unsaturation 0.005mmol/g poly(propylene oxide) ether dibasic alcohol
PPG1000 number-average molecular weight 10000, degree of unsaturation 0.005mmol/g poly(propylene oxide) ether dibasic alcohol
PPG3000 number-average molecular weight 30000, degree of unsaturation 0.005mmol/g poly(propylene oxide) ether dibasic alcohol
PPG3600 number-average molecular weight 6000, proportion of primary OH groups 70%, ring poly(propylene oxide) ether trivalent alcohol
MDI-100 4,4 '-diphenylmethanediisocyanate
MDI-50 4,4 '-diphenylmethanediisocyanate 50%, 2,4 '-diphenylmethanediisocyanate 50%
MOCA 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane
TDI-80 2,4 toluene diisocyanate 80%, 2,6-tolylene diisocyanate 20%
Embodiment 1:
Polymeric constituent: the polyether glycol (PPG3600) 39.5% of the polyether glycol (PPG2000) 30% of functionality 2, molecular weight 2000, functionality 3, molecular weight 6000,3,3 '-two chloro-4,4 '-diaminodiphenyl-methane (MOCA) 30%, mercury catalyst 0.5% prepare according to the method for the invention.
Prepolymer: be polyether glycol (PPG1000) 55%, diphenylmethanediisocyanate (MDI-100) 40% with 2 functionality, molecular weight 1000, tolylene diisocyanate (TDI-80) 5% 70 ℃～90 ℃ reaction 2～3 little vacuum (-0.095MPa) remove bubble, obtain isocyano-content and be 10% prepolymer.
Prepolymer and polymeric constituent are with the mixed of 1:1, and mixing temperature is 25 ℃～40 ℃, and the goods curing temperature is 70 ℃～100 ℃, vulcanize 20 minutes, obtain the polyurethane elastomer goods.
Embodiment 2:
Polymeric constituent: the polyether glycol (PPG3000) 81% of functionality 2, molecular weight 3000,3,3 '-two chloro-4,4 '-diaminodiphenyl-methane (MOCA) 18%, bismuth catalyst 1.0%.
Prepolymer: be polyether glycol (PPG2000) 66%, diphenylmethanediisocyanate (MDI-50) 36% with 2 functionality, molecular weight 2000, tolylene diisocyanate (TDI-80) 8% 70 ℃～90 ℃ reaction 2～3 little vacuum (-0.095MPa) remove bubble, obtain isocyano-content and be 13% prepolymer.
Prepolymer and polymeric constituent are with the mixed of 1:1, and mixing temperature is 25 ℃～40 ℃, and the goods curing temperature is 70 ℃～100 ℃, vulcanize 20 minutes, obtain the polyurethane elastomer goods.
Embodiment 3:
Prepolymer: be polyether glycol (PPG1000) 67.6%, diphenylmethanediisocyanate (MDI-100) 22.4% with 2 functionality, molecular weight 1000, tolylene diisocyanate (TDI-80) 10% 70 ℃～90 ℃ reaction 2～3 little vacuum (-0.095MPa) remove bubble, obtain isocyano-content and be 5% prepolymer.。
Solidifying agent be selected from 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane (MOCA)
Prepolymer and MOCA carry out hybrid reaction with the equivalence ratio of 0.9 NH2/NCO, mixing temperature is 75 ℃～90 ℃, and the goods curing temperature is 100 ℃～115 ℃, vulcanizes the demoulding in 20～60 minutes, 100 ℃～115 ℃ postcure 8～10 hours, obtain the polyurethane elastomer goods.
Comparison example: be polyether glycol (PPG1000) 76%, tolylene diisocyanate (TDI-80) 24%, obtain the performed polymer of isocyano-content 5% with 2 functionality, molecular weight 1000.
Solidifying agent be selected from 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane (MOCA), prepolymer and MOCA are with 0.9 NH
2The equivalence ratio of/NCO is reacted, and mixing temperature is 75 ℃～90 ℃, and the goods curing temperature is 100 ℃～115 ℃, vulcanizes the demoulding in 20～60 minutes, 100 ℃～115 ℃ postcure 8～10 hours, obtains the polyurethane elastomer goods.
Polyurethane elastomer product properties such as following table:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparison example |
| Hardness (Shao A) | 95 | 80 | 90 | 90 |
| Tensile strength (Mpa) | 27 | 18 | 25 | 21 |
| Elongation % | 480 | 600 | 520 | 480 |
| Tear strength (KN/m) | 78 | 55 | 63 | 57 |
| Resilience % | 30 | 45 | 30 | 25 |
Claims (4)
1, a kind of pouring type urethane elastomer composition is characterized in that being made up of two kinds of components:
A component: a kind of prepolymer, obtain according to the method for being prepared as follows: by weight percentage, reacted 2～3 hours at 70 ℃～90 ℃ by vulcabond 25%～35% and polyether glycol 65%～75%, obtain isocyano-content and be 4～6% prepolymer, it is 2 or 3 that described polyether glycol adopts functionality, the poly(propylene oxide) ethoxylated polyhydric alcohol of number-average molecular weight in 1000～3000 scopes, described vulcabond is made up of diphenylmethanediisocyanate and tolylene diisocyanate blend, and wherein tolylene diisocyanate accounts for 5%～50% of blend vulcabond gross weight;
The B component: a kind of aromatic diamine solidifying agent, be selected from 3,3 '-dichloro-4,4 '-diaminodiphenyl-methane or 3,5-diformazan sulfenyl tolylene diamine.
2, pouring type urethane elastomer composition according to claim 1 is characterized in that tolylene diisocyanate accounts for 5%～20% of blend vulcabond gross weight in the described A component.
3, a kind of pouring type urethane elastomer composition is characterized in that being made up of two kinds of components:
C component: a kind of prepolymer, obtain according to the method for being prepared as follows: by weight percentage, reacted 2～3 hours at 70 ℃～90 ℃ by vulcabond 30%～50% and polyether glycol 50%～70%, obtain isocyano-content and be 8～14% prepolymer, it is 2 or 3 that described polyether glycol adopts functionality, the poly(propylene oxide) ethoxylated polyhydric alcohol of number-average molecular weight in 1000～3000 scopes, described vulcabond is made up of diphenylmethanediisocyanate and tolylene diisocyanate blend, and wherein tolylene diisocyanate accounts for 5%～20% of blend vulcabond gross weight;
D component: a kind of polymeric constituent, obtain according to the method for being prepared as follows: by weight percentage, with functionality is 2 or 3, the poly(propylene oxide) ethoxylated polyhydric alcohol 69.5%～81% of molecular weight in 1000～3000 scopes, aromatic diamine solidifying agent 18%～30%, catalyzer 0.2%～1%, at 100～110 ℃, dewater below-the 0.095MPa to moisture less than 0.05%, obtain polymeric constituent, wherein catalyzer is selected from dibutyl tin laurate, organic lead, organo-bismuth, organic zinc, in the organic mercury one or more, the aromatic diamine solidifying agent is selected from 3,3 '-dichloro-4,4 '-diaminodiphenyl-methane or 3,5-diformazan sulfenyl tolylene diamine.
4, pouring type urethane elastomer composition according to claim 3 is characterized in that tolylene diisocyanate accounts for 5%～20% of blend vulcabond gross weight in the described C component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101138803A CN100500762C (en) | 2007-09-29 | 2007-09-29 | Pouring type urethane elastomer composition |
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| CNB2007101138803A CN100500762C (en) | 2007-09-29 | 2007-09-29 | Pouring type urethane elastomer composition |
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| CN101165095A CN101165095A (en) | 2008-04-23 |
| CN100500762C true CN100500762C (en) | 2009-06-17 |
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| CN106046313A (en) * | 2016-06-03 | 2016-10-26 | 湖北鼎龙化学股份有限公司 | Chemical-mechanical polishing pad, buffer layer and preparation method of buffer layer |
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Owner name: SHANGHAI DONGDA POLYURETHANE CO., LTD. Free format text: FORMER OWNER: SHANDONG DONGDA YINUOWEI POLYURETHANE CO.LTD. Effective date: 20091113 |
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Effective date of registration: 20091113 Address after: Shanghai City, Jinshan District Shanyang Zhen Ning Road No. 307 Patentee after: Shanghai Dongda Polyurethane Co., Ltd. Address before: No. 109, Tai Mo Road, hi tech Development Zone, Shandong, Zibo Patentee before: Shangdong Dong Da Inov Polyuerthane Co., Ltd. |
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Granted publication date: 20090617 Termination date: 20160929 |
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