CN106589292A - High-rigidity and slow-gelling polyurethane elastomer and preparation method thereof - Google Patents
High-rigidity and slow-gelling polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN106589292A CN106589292A CN201611257913.7A CN201611257913A CN106589292A CN 106589292 A CN106589292 A CN 106589292A CN 201611257913 A CN201611257913 A CN 201611257913A CN 106589292 A CN106589292 A CN 106589292A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a high-rigidity and slow-gelling polyurethane elastomer and a preparation method thereof and belongs to the technical field of polyurethane application. The high-rigidity and slow-gelling polyurethane elastomer provided by the invention is composed of a component A and a component B, and the weight ratio of the component A to the component B is 100 to (23-43), wherein (1) the component A is a polyurethane pre-polymer and is prepared from the following raw materials: 35.6%-62.5% by weight of polyatomic alcohol and 37.5%-64.4% by weight of diisocyanate; the degree of functionality of the polyatomic alcohol is 2 and the number average molecular weight of the polyatomic alcohol is 90-1000; the diisocyanate is a mixture of aliphatic diisocyanate and aromatic diisocyanate; and (2) the component B is a chain extender. By adopting the high-rigidity and slow-gelling polyurethane elastomer provided by the invention, the gelling time of a high-rigidity product is prolonged, the in-kettle service life is prolonged and the operation time is prolonged; the high-rigidity and slow-gelling polyurethane elastomer is used for preparing high-rigidity large-size products; and meanwhile, the invention provides the simple and feasible preparation method.
Description
Technical field
The present invention relates to a kind of high rigidity slow hardening glue polyurethane elastomer and preparation method thereof, belongs to polyurethane application technology
Field.
Background technology
Polyurethane elastomer is a kind of macromolecular material between rubber and plastics, combines caoutchouc elasticity and plastic hardness
Advantage, while its mechanical performance anti-wear performance is excellent with rebound performance, be widely used in life, automobile, household electrical appliances etc. each
Individual field.
Polyurethane elastomer is made up of in structure hard section with soft section, can be prepared by adjusting the ratio of hard section and soft section
The product of different hardness, prepares performed polymer of the high hardness polyurethane product needed using high isocyano-content, but with cyanogen
The increase of acid group content, the gel time of performed polymer is greatly shortened, and is only used for the production of small pieces, it is difficult to for big part product
The preparation of product.
The content of the invention
It is an object of the invention to provide a kind of high rigidity slow hardening glue polyurethane elastomer, it extends the solidifying of high rigidity product
The glue time, the life-span in kettle is improve, extend the operating time, can be used for preparing the big part product of high rigidity；The present invention is carried simultaneously
Simple preparation method is supplied.
High rigidity slow hardening glue polyurethane elastomer of the present invention, is made up of component A and B component, A, the weight of B component
Than for 100：23～43, wherein：
(1) component A is polyurethane prepolymer, is made up of the raw material of following weight percentage：
Polyhydric alcohol 35.6～62.5%
Diisocyanate 37.5～64.4%；
The degree of functionality of the polyhydric alcohol is 2, and number-average molecular weight is 90～1000；
The diisocyanate is aliphatic isocyanates and the mixture of aromatic isocyanate, aliphatic isocyanates
For the 30～100% of diisocyanate gross mass；
(2) B component is chain extender.
The polyhydric alcohol and diisocyanate react 2～3 hours at 85 DEG C～95 DEG C, obtain isocyano-content for 8～
15% prepolymer.
The polyhydric alcohol is in PTMG650, PTMG1000, BDO, DEG, PPG 400, PPG 1000 or PE-2010
Plant or various.
The aliphatic isocyanates are to hydrogenate one or more in MDI, IPDI or HDI.
The aromatic isocyanate is one or more in T-80, T-100, MDI-50, MDI-100, liquefied mdi.
The chain extender is MOCA or E-300.
Described high rigidity slow hardening glue method for preparing polyurethane elastic body, is to mix component A with B component, is poured into
In mould that is warmed-up and scribbling releasing agent, matched moulds during gel point to be achieved, demoulding time at 30～60 minutes, after cure 10～
16 hours, described high rigidity slow hardening glue polyurethane elastomer is obtained.
The component A temperature is 60～70 DEG C, and the temperature of B component is 25～120 DEG C.
The mould is preheated to 100 DEG C～120 DEG C.
Described aliphatic isocyanates reactivity is low, and in prepared by performed polymer a certain amount of aliphatic Carbimide. is added
Ester can extend the gel time of performed polymer, improve the life-span in performed polymer kettle.
The invention has the advantages that：
(1) high rigidity slow hardening glue polyurethane elastomer of the present invention, extends the gel time of high rigidity product, carries
In the life-span in high kettle, extend the operating time, can be used for preparing the big part product of high rigidity, the polyurethane elastomer of preparation it is hard
Degree is in 60～83D of Shao；
(2) high rigidity slow hardening glue method for preparing polyurethane elastic body of the present invention, simple, beneficial to industrialization
Production.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but it is not intended to limit the enforcement of the present invention.
Material therefor is as follows：
Embodiment 1
Prepolymer：PolyTHF dihydroxylic alcohols PTMG 650 62.5%, T-80 26.2%, hydrogenation MDI 11.3% are 95
DEG C reaction 3 hours vacuum (- 0.095MPa) removing bubble, obtain the prepolymer that isocyano-content is 8%.
Prepolymer is heated up to 60 DEG C and MOCA with 100/23 ratio mix homogeneously, and it is 120 DEG C to be poured into mold temperature
In mould, urethane cure times are 4min, and product is molded for 30 minutes, after cure 16 hours in 100 DEG C of environment, and obtaining hardness is
The polyurethane elastomer product of Shao D67.
Embodiment 2
Prepolymer：Polyether Glycols PPG 1,000 28%, PPG 400 28%, hydrogenation MDI 17.6%, T-100
26.4%, in 85 DEG C of reactions, 3 hours vacuum (- 0.095MPa) removing bubbles, obtains the prepolymer that isocyano-content is 10%.
Prepolymer is heated up to 60 DEG C and MOCA with 100/28.6 ratio mix homogeneously, is poured into mold temperature for 120 DEG C
Mould in, urethane cure times are 5min, and product is molded for 30 minutes, and after cure 16 hours, obtain hardness in 100 DEG C of environment
For the polyurethane elastomer product of Shao D75.
Embodiment 3
Prepolymer：Polyester diol PE-2010 47.7%, DEG 4.7%, IPDI 23.8%, T-100 23.8% exist
95 DEG C of reactions, 2 hours vacuum (- 0.095MPa) removing bubbles, obtain the prepolymer that isocyano-content is 12.5%.
Prepolymer is heated up to 70 DEG C and E-300 with 100/29 ratio mix homogeneously, and it is 120 DEG C to be poured into mold temperature
In mould, urethane cure times are 7min, and product is molded for 60 minutes, after cure 16 hours in 100 DEG C of environment, and obtaining hardness is
The polyurethane elastomer product of Shao D79.
Embodiment 4
Prepolymer：PolyTHF dihydroxylic alcohols PTMG 650 40.3%, BDO 1.2%, hydrogenation MDI 41%, T-100
17.5%, in 95 DEG C of reactions, 2.5 hours vacuum (- 0.095MPa) removing bubbles, obtain the pre-polymerization that isocyano-content is 15%
Thing.
Prepolymer is heated up to 60 DEG C and MOCA with 100/43 ratio mix homogeneously, and it is 120 DEG C to be poured into mold temperature
In mould, urethane cure times are 8min, and product is molded for 60 minutes, after cure 16 hours in 100 DEG C of environment, and obtaining hardness is
The polyurethane elastomer product of Shao D83.
Embodiment 5
Prepolymer：PolyTHF dihydroxylic alcohols PTMG 650 34.5%, BDO 11.9%, hydrogenation MDI 64.4%, 95
DEG C reaction 3 hours vacuum (- 0.095MPa) removing bubble, obtain the prepolymer that isocyano-content is 15%.
Prepolymer is heated up to 60 DEG C and MOCA with 100/43 ratio mix homogeneously, and it is 120 DEG C to be poured into mold temperature
In mould, urethane cure times are 11min, and product is molded for 60 minutes, and after cure 16 hours, obtain hardness in 100 DEG C of environment
For the polyurethane elastomer product of Shao D83.
Comparative example 1
Prepolymer：Polyether Glycols PPG 1,000 30.2%, PPG 400 30.2%, T-100 35.6% are anti-at 85 DEG C
2 hours vacuum (- 0.095MPa) removing bubbles are answered, the prepolymer that isocyano-content is 10% is obtained.
Prepolymer is heated up to 60 DEG C and MOCA with 100/28.6 ratio mix homogeneously, is poured into mold temperature for 120 DEG C
Mould in, urethane cure times are 2min, and product is molded for 30 minutes, and after cure 16 hours, obtain hardness in 100 DEG C of environment
For the polyurethane elastomer product of Shao D75.
The performance test results of above example and comparative example are shown in Table 1.
The performance test results of the embodiment of table 1 and comparative example
Claims (9)
1. a kind of high rigidity slow hardening glue polyurethane elastomer, it is characterised in that：It is made up of component A and B component, A, the weight of B component
Amount is than being 100：23～43, wherein：
(1) component A is polyurethane prepolymer, is made up of the raw material of following weight percentage：
Polyhydric alcohol 35.6～62.5%
Diisocyanate 37.5～64.4%；
The degree of functionality of the polyhydric alcohol is 2, and number-average molecular weight is 90～1000；
The diisocyanate is the mixture of aliphatic isocyanates and aromatic isocyanate, and aliphatic isocyanates are two
The 30～100% of isocyanates gross mass；
(2) B component is chain extender.
2. high rigidity slow hardening glue polyurethane elastomer according to claim 1, it is characterised in that：Polyhydric alcohol and two Carbimide .s
Ester reacts 2～3 hours at 85 DEG C～95 DEG C, obtains the prepolymer that isocyano-content is 8～15%.
3. high rigidity slow hardening glue polyurethane elastomer according to claim 1, it is characterised in that：Polyhydric alcohol be PTMG650,
One or more in PTMG1000, BDO, DEG, PPG 400, PPG 1000 or PE-2010.
4. high rigidity slow hardening glue polyurethane elastomer according to claim 1, it is characterised in that：Aliphatic isocyanates are
One or more in hydrogenation MDI, IPDI or HDI.
5. high rigidity slow hardening glue polyurethane elastomer according to claim 1, it is characterised in that：Aromatic isocyanate is
One or more in T-80, T-100, MDI-50, MDI-100, liquefied mdi.
6. high rigidity slow hardening glue polyurethane elastomer according to claim 1, it is characterised in that：Chain extender is MOCA or E-
300。
7. the arbitrary described high rigidity slow hardening glue method for preparing polyurethane elastic body of a kind of claim 1-6, it is characterised in that：
Component A mixes with B component, in being poured into mould that is warmed-up and scribbling releasing agent, matched moulds during gel point to be achieved, and demoulding time
At 30～60 minutes, after cure 10～16 hours was obtained described high rigidity slow hardening glue polyurethane elastomer.
8. high rigidity slow hardening glue method for preparing polyurethane elastic body according to claim 7, it is characterised in that：Component A
Temperature is 60～70 DEG C, and the temperature of B component is 25～120 DEG C.
9. high rigidity slow hardening glue method for preparing polyurethane elastic body according to claim 7, it is characterised in that：Mould is pre-
Heat is to 100 DEG C～120 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611257913.7A CN106589292A (en) | 2016-12-30 | 2016-12-30 | High-rigidity and slow-gelling polyurethane elastomer and preparation method thereof |
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| CN201611257913.7A CN106589292A (en) | 2016-12-30 | 2016-12-30 | High-rigidity and slow-gelling polyurethane elastomer and preparation method thereof |
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Family
ID=58583177
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| CN201611257913.7A Pending CN106589292A (en) | 2016-12-30 | 2016-12-30 | High-rigidity and slow-gelling polyurethane elastomer and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240686A (en) * | 2019-04-29 | 2019-09-17 | 山西科灜科技有限公司 | A kind of high-performance high-hard, transparent polyurethane elastomer and preparation method thereof |
| CN110437411A (en) * | 2019-08-09 | 2019-11-12 | 沈金城 | A kind of high hardness polyurethane and preparation method thereof |
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| CN105461896A (en) * | 2016-01-19 | 2016-04-06 | 黎明化工研究设计院有限责任公司 | High-hardness polyurethane elastomer pressure-bearing support material for bridge and preparation method and using method thereof |
| CN105504212A (en) * | 2016-01-22 | 2016-04-20 | 武汉理工大学 | Preparation method of damp-heat-ageing-resistant polyurethane elastomer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240686A (en) * | 2019-04-29 | 2019-09-17 | 山西科灜科技有限公司 | A kind of high-performance high-hard, transparent polyurethane elastomer and preparation method thereof |
| CN110437411A (en) * | 2019-08-09 | 2019-11-12 | 沈金城 | A kind of high hardness polyurethane and preparation method thereof |
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Application publication date: 20170426 |