CN108034226A - A kind of high wear-resistant thermoplastic polyurethane elastomer and preparation method thereof - Google Patents
A kind of high wear-resistant thermoplastic polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN108034226A CN108034226A CN201711441283.3A CN201711441283A CN108034226A CN 108034226 A CN108034226 A CN 108034226A CN 201711441283 A CN201711441283 A CN 201711441283A CN 108034226 A CN108034226 A CN 108034226A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- 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
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- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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Abstract
The invention discloses a kind of high wear-resistant thermoplastic method for preparing polyurethane elastic body, include the following steps：Step 1：Polyester diol and the preparation of Isosorbide-5-Nitrae mixture of butanediols, by polyester diol and Isosorbide-5-Nitrae butanediol by weight 100:15‑100:40 mixing, add micro silicone oil, in 80 90 DEG C be sufficiently stirred 0.5 1 it is small when, obtain the mixture of polyester diol and Isosorbide-5-Nitrae butanediol；Step 2：By the mixture of step 1 and 4, the 4' methyl diphenylene diisocyanates equivalent to mixture weight 50 90% and micro octoate catalyst stannous hybrid reaction, polyurethane elastomer is obtained.The object of the present invention is to provide a kind of fuel-displaced flour extraction it is low, there is low high wear-resistant thermoplastic polyurethane elastomer of good basic wearability, auxiliary agent eduction rate and preparation method thereof.
Description
Technical field
The present invention relates to polyurethane field, specifically, is related to a kind of high wear-resistant thermoplastic polyurethane elastomer and its system
Preparation Method.
Background technology
Although thermoplastic polyurethane elastomer itself has good wear-resisting property, in some special application fields,
Such as pu tire, wear resistant belt and footwear material, the wear-resisting property of general plastic polyurethane elastomeric material can not still meet should
Use demand.How to obtain friction coefficient is low, physical property is good, in product service life without it is fuel-displaced go out powder thermoplastic polyurethane
Elastomer is the key for solving this application field.
Improving the main means of polyurethane elastomer at present is：1. increasing hard section ratio when being formulated and designing, strengthen poly- ammonia
The physical property of ester elastomer；2. substantial amounts of ethylene bis stearamide series lubricant agent is added in production to reduce elastic polyurethane
The friction coefficient of body；3. it is mixed and modified with other plastics, to improve the resistance to of polyurethane elastomer by the characteristic of other plastics
Mill property.
Then these means also bring other problems to polyurethane elastomer：1. strengthen the thing of polyurethane elastomer simply
On the one hand rationality can require the processing temperature of higher, influence the processing of product, add energy consumption and equipment loss；The opposing party
The injection molding cycle that the stronger physical property in face typically results in polyurethane elastomer is longer, reduces production efficiency.2. excessive second
Support bis-stearamides series lubricant agent addition can make product it is fuel-displaced go out powder risk greatly improve, influence the use of product.3. by
In the particularity of polyurethane elastomer, it is poor with most of Compatibility in Plastics.Once, characteristic mixed and modified with other plastics
Performance must plummet, while may also lose the environmental protection characteristic of polyurethane elastomer.
The content of the invention
It is low, low with good basic wearability, auxiliary agent eduction rate the object of the present invention is to provide a kind of fuel-displaced flour extraction
High wear-resistant thermoplastic polyurethane elastomer and preparation method thereof.
The technical scheme is that：A kind of high wear-resistant thermoplastic method for preparing polyurethane elastic body, including following step
Suddenly：
Step 1：Polyester diol and the preparation of 1,4-butanediol mixture, by polyester diol and 1,4-butanediol by weight
Measure ratio 100:15-100:40 mixing, add micro silicone oil, in 80-90 DEG C be sufficiently stirred 0.5-1 it is small when, obtain polyester binary
The mixture of alcohol and 1,4- butanediols；
Step 2：By the mixture of step 1 and different equivalent to the 4,4'- diphenyl methanes two of mixture weight 50-90%
Cyanate and micro octoate catalyst stannous hybrid reaction, obtain polyurethane elastomer.
In above-mentioned high wear-resistant thermoplastic method for preparing polyurethane elastic body, step is further included after the step 2
Rapid 3：
The polyurethane elastomer of step 2 is mixed with the silicone master batch of the 3-5 ‰ equivalent to elastic polyurethane body weight,
90-110 DEG C is dried a period of time, you can injection-molded item.
In above-mentioned high wear-resistant thermoplastic method for preparing polyurethane elastic body, the use of the silicone oil in the step 1
Amount accounts for the 3-7 ‰ of mixture total weight.
In above-mentioned high wear-resistant thermoplastic method for preparing polyurethane elastic body, the silicone oil is linear non-reactive
Dimethyl silicone polymer, molecular weight is between 7000-12000.
In above-mentioned high wear-resistant thermoplastic method for preparing polyurethane elastic body, the polyester diol for gather oneself two
Sour ethylene glycol -1,4- butyl glycol ester diols；Molecular weight is 2000-3000.
In above-mentioned high wear-resistant thermoplastic method for preparing polyurethane elastic body, in the step 2, octoate catalyst
0.04-0.08 ‰ of the dosage of stannous equivalent to mixture total weight.
In above-mentioned high wear-resistant thermoplastic method for preparing polyurethane elastic body, the reaction condition of the step 2 is
75-85 DEG C of initial reaction temperature, curing 48-72 it is small when after crush, be granulated through comminutor.
In above-mentioned high wear-resistant thermoplastic method for preparing polyurethane elastic body, the silicone master batch is by 50% molecule
Measure the linear non-reactive dimethyl silicone polymer between 20000-30000,49.5% polyethylene support and 0.5% idol
Connection agent mixing granulator forms.
Meanwhile the invention also discloses a kind of high wear-resistant thermoplastic polyurethane elastomer, using method system as described above
It is standby to obtain.
Beneficial effects of the present invention are as follows：
Polyester diol used in the present invention is polyadipate ethylene glycol -1,4-butanediol esterdiol, molecular weight 2000-
3000.Polyadipate ethylene glycol -1,4- butyl glycol ester diol synthesis of polyurethane elastomers it is fuel-displaced go out powder risk compared with polyadipate -
1,4- butyl glycol ester diols are low.Molecular weight 2000-3000 ensures that synthesis of polyurethane elastomer is specific good basic wear-resisting.Poly- ammonia
The silicone oil of addition 5 ‰ can allow polyurethane elastomer to obtain relatively low friction coefficient when ester elastomer synthesizes, simultaneously as plus
It is few to enter amount, it is ensured that product there will not be auxiliary agent precipitation in service life.
As a further improvement on the present invention, the silicone master batch of 3-5 ‰ is added again in injection, you can further to increase
The wearability of product, can also make up loss of physical properties caused by auxiliary agent addition, and final stable acquisition is wear-resisting to be less than 30mm3
(test method is：53516 GB of DIN, 9867 abrasion resistance test methods) polyurethane elastomer.
Embodiment
With reference to embodiment, technical scheme is described in further detail, but is not formed pair
Any restrictions of the present invention.
Specific embodiment 1：
Polyester diol and the preparation of 1,4- mixture of butanediols：Polyester diol and 1,4- butanediols are pressed 100:15 is mixed
Close, add 5 ‰ silicone oil, in 80-90 DEG C be sufficiently stirred 0.5-1 it is small when, obtain the mixing of polyester diol and 1,4-butanediol
Thing.The silicone oil is linear non-reactive dimethyl silicone polymer, and for molecular weight between 7000-12000, molecular structure is as follows：
Polyester polyol is polyadipate ethylene glycol -1,4- butyl glycol ester diols；Molecular weight is 2000-3000.
The 4,4'- diphenyl methanes of mixture weight 50% are added into the mixture of polyester diol and 1,4- butanediols
Diisocyanate and 0.06 ‰ octoate catalyst stannous, are sufficiently stirred reaction, 80 DEG C of initial reaction temperature, when curing 60 is small after
It is broken, it is granulated through comminutor, obtains the polyurethane elastomer that shore hardness is 90A-64D.
Polyurethane elastomer is mixed with 4 ‰ silicone master batch, when 100 DEG C of bakings 2 are small, you can injection-molded item.The silicon
Linear non-reactive dimethyl silicone polymer of the ketone master batch by 50% molecular weight between 20000-30000,49.5% poly- second
Alkene carrier and 0.5% coupling agent mixing granulator form.A small amount of coupling agent can be different with remnants after adding polyurethane elastomer
Cyanate radical cross-linking reaction, makes up because auxiliary agent addition causes the decline of polyurethane elastomer physical property to a certain extent.
Specific embodiment 2
Polyester diol and the preparation of 1,4- mixture of butanediols：Polyester diol and 1,4- butanediols are pressed 100:40 is mixed
Close, add 5 ‰ silicone oil, in 80-90 DEG C be sufficiently stirred 1 it is small when, obtain the mixture of polyester diol and 1,4-butanediol.Institute
It is linear non-reactive dimethyl silicone polymer to state silicone oil, and for molecular weight between 7000-12000, molecular structure is as follows：
Polyester polyol is polyadipate ethylene glycol -1,4- butyl glycol ester diols；Molecular weight is 2000-3000.
The 4,4'- diphenyl methanes of mixture weight 90% are added into the mixture of polyester diol and 1,4- butanediols
Diisocyanate and 0.06 ‰ octoate catalyst stannous, are sufficiently stirred reaction, 85 DEG C of initial reaction temperature, when curing 70 is small after
It is broken, it is granulated through comminutor, obtains the polyurethane elastomer that shore hardness is 90A-64D.
Polyurethane elastomer is mixed with 5 ‰ silicone master batch, when 110 DEG C of bakings 2 are small, you can injection-molded item.The silicon
Linear non-reactive dimethyl silicone polymer of the ketone master batch by 50% molecular weight between 20000-30000,49.5% poly- second
Alkene carrier and 0.5% coupling agent mixing granulator form.A small amount of coupling agent can be different with remnants after adding polyurethane elastomer
Cyanate radical cross-linking reaction, makes up because auxiliary agent addition causes the decline of polyurethane elastomer physical property to a certain extent.
Specific embodiment 3
Polyester diol and the preparation of 1,4- mixture of butanediols：Polyester diol and 1,4- butanediols are pressed 100:30 is mixed
Close, add 7 ‰ silicone oil, in 80-90 DEG C be sufficiently stirred 1 it is small when, obtain the mixture of polyester diol and 1,4-butanediol.Institute
It is linear non-reactive dimethyl silicone polymer to state silicone oil, and for molecular weight between 7000-12000, molecular structure is as follows：
Polyester polyol is polyadipate ethylene glycol -1,4- butyl glycol ester diols；Molecular weight is 2000-3000.
The 4,4'- diphenyl methanes of mixture weight 70% are added into the mixture of polyester diol and 1,4- butanediols
Diisocyanate and 0.04 ‰ octoate catalyst stannous, are sufficiently stirred reaction, 85 DEG C of initial reaction temperature, when curing 70 is small after
It is broken, it is granulated through comminutor, obtains the polyurethane elastomer that shore hardness is 90A-64D.
Polyurethane elastomer is mixed with 5 ‰ silicone master batch, when 110 DEG C of bakings 2 are small, you can injection-molded item.The silicon
Linear non-reactive dimethyl silicone polymer of the ketone master batch by 50% molecular weight between 20000-30000,49.5% poly- second
Alkene carrier and 0.5% coupling agent mixing granulator form.A small amount of coupling agent can be different with remnants after adding polyurethane elastomer
Cyanate radical cross-linking reaction, makes up because auxiliary agent addition causes the decline of polyurethane elastomer physical property to a certain extent.
Specific embodiment 4
Polyester diol and the preparation of 1,4- mixture of butanediols：Polyester diol and 1,4- butanediols are pressed 100:20 is mixed
Close, add 4 ‰ silicone oil, in 80-90 DEG C be sufficiently stirred 1 it is small when, obtain the mixture of polyester diol and 1,4-butanediol.Institute
It is linear non-reactive dimethyl silicone polymer to state silicone oil, and for molecular weight between 7000-12000, molecular structure is as follows：
Polyester polyol is polyadipate ethylene glycol -1,4- butyl glycol ester diols；Molecular weight is 2000-3000.
The 4,4'- diphenyl methanes of mixture weight 60% are added into the mixture of polyester diol and 1,4- butanediols
Diisocyanate and 0.08 ‰ octoate catalyst stannous, are sufficiently stirred reaction, 75 DEG C of initial reaction temperature, when curing 50 is small after
It is broken, it is granulated through comminutor, obtains the polyurethane elastomer that shore hardness is 90A-64D.
Polyurethane elastomer is mixed with 3 ‰ silicone master batch, when 110 DEG C of bakings 2 are small, you can injection-molded item.The silicon
Linear non-reactive dimethyl silicone polymer of the ketone master batch by 50% molecular weight between 20000-30000,49.5% poly- second
Alkene carrier and 0.5% coupling agent mixing granulator form.A small amount of coupling agent can be different with remnants after adding polyurethane elastomer
Cyanate radical cross-linking reaction, makes up because auxiliary agent addition causes the decline of polyurethane elastomer physical property to a certain extent.
Above-described is only presently preferred embodiments of the present invention, all timess made in the range of the spirit and principles in the present invention
What modifications, equivalent substitutions and improvements etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of high wear-resistant thermoplastic method for preparing polyurethane elastic body, it is characterised in that include the following steps：
Step 1：The preparation of polyester diol and 1,4-butanediol mixture, by polyester diol and 1,4-butanediol by weight
100:15-100:40 mixing, add micro silicone oil, in 80-90 DEG C be sufficiently stirred 0.5-1 it is small when, obtain polyester diol with
The mixture of 1,4- butanediols；
Step 2：By the mixture of step 1 and 4,4'- diphenylmethane diisocyanates equivalent to mixture weight 50-90%
Ester and micro octoate catalyst stannous hybrid reaction, obtain polyurethane elastomer.
2. high wear-resistant thermoplastic method for preparing polyurethane elastic body according to claim 1, it is characterised in that described
Step 3 is further included after step 2：
The polyurethane elastomer of step 2 is mixed with the silicone master batch of the 3-5 ‰ equivalent to elastic polyurethane body weight, 90-110
DEG C dry a period of time, you can injection-molded item.
3. high wear-resistant thermoplastic method for preparing polyurethane elastic body according to claim 1 or 2, it is characterised in that institute
The dosage of silicone oil in the step 1 stated accounts for the 3-7 ‰ of mixture total weight.
4. high wear-resistant thermoplastic method for preparing polyurethane elastic body according to claim 3, it is characterised in that described
Silicone oil is linear non-reactive dimethyl silicone polymer, and molecular weight is between 7000-12000.
5. high wear-resistant thermoplastic method for preparing polyurethane elastic body according to claim 1 or 2, it is characterised in that institute
The polyester diol stated is polyadipate ethylene glycol -1,4- butyl glycol ester diols；Molecular weight is 2000-3000.
6. high wear-resistant thermoplastic method for preparing polyurethane elastic body according to claim 1 or 2, it is characterised in that institute
In the step 2 stated, the 0.04-0.08 ‰ of the dosage of octoate catalyst stannous equivalent to mixture total weight.
7. high wear-resistant thermoplastic method for preparing polyurethane elastic body according to claim 6, it is characterised in that described
The reaction condition of step 2 is 75-85 DEG C of initial reaction temperature, curing 48-72 it is small when after crush, be granulated through comminutor.
8. high wear-resistant thermoplastic method for preparing polyurethane elastic body according to claim 2, it is characterised in that described
Linear non-reactive dimethyl silicone polymer of the silicone master batch by 50% molecular weight between 20000-30000,49.5% is poly-
Ethene carrier and 0.5% coupling agent mixing granulator form.
9. a kind of high wear-resistant thermoplastic polyurethane elastomer, it is characterised in that using the method as described in claim 1-8 is any
It is prepared.
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Cited By (4)
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| CN109233255A (en) * | 2018-09-21 | 2019-01-18 | 宁波雅致机械有限公司 | A kind of stable high abrasion compound polyurethane material and preparation method thereof |
| CN109337355A (en) * | 2018-09-11 | 2019-02-15 | 东莞市吉鑫高分子科技有限公司 | A kind of high scratch resistance thermoplastic polyurethane elastomer and preparation method thereof |
| CN112533992A (en) * | 2018-08-03 | 2021-03-19 | 艾维恩股份有限公司 | Bloomless thermoplastic polyurethane compounds and thermoplastic articles molded therefrom |
| CN113637315A (en) * | 2021-07-27 | 2021-11-12 | 上海永利输送***有限公司 | Middle tooth type wireless core conveyor belt |
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| CN109337355A (en) * | 2018-09-11 | 2019-02-15 | 东莞市吉鑫高分子科技有限公司 | A kind of high scratch resistance thermoplastic polyurethane elastomer and preparation method thereof |
| CN109337355B (en) * | 2018-09-11 | 2021-10-22 | 东莞市吉鑫高分子科技有限公司 | High-scratch-resistance thermoplastic polyurethane elastomer and preparation method thereof |
| CN109233255A (en) * | 2018-09-21 | 2019-01-18 | 宁波雅致机械有限公司 | A kind of stable high abrasion compound polyurethane material and preparation method thereof |
| CN113637315A (en) * | 2021-07-27 | 2021-11-12 | 上海永利输送***有限公司 | Middle tooth type wireless core conveyor belt |
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