CN109970946A - A kind of preparation method of environmental protection low hardness polyurethane elastic body - Google Patents
A kind of preparation method of environmental protection low hardness polyurethane elastic body Download PDFInfo
- Publication number
- CN109970946A CN109970946A CN201711448439.0A CN201711448439A CN109970946A CN 109970946 A CN109970946 A CN 109970946A CN 201711448439 A CN201711448439 A CN 201711448439A CN 109970946 A CN109970946 A CN 109970946A
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- elastic body
- low hardness
- diisocyanate
- polyurethane elastic
- 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.)
- Pending
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Classifications
-
- 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
-
- 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
- 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
-
- 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
- C08G18/70—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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to polyurethane elastomer preparation technical fields, more particularly to a kind of environment-friendly type low hardness polyurethane elastic body and preparation method thereof of not plasticizer-containing, environmentally friendly low hardness polyurethane elastic body in the present invention, by polyalcohol, isocyanates, chain extender, dissaving polymer, antioxidant, anti- UV agent, catalyst composition synthesizes two steps by performed polymer synthesis and elastomer, finally obtains the low hardness polyurethane elastic body material of environmental protection.Low hardness polyurethane elastic body of the invention has the advantages that nontoxic, pollution-free, stable structure, excellent in mechanical performance, can be used for and the footwear material of human contact, medical treatment, the fields such as physical fitness.
Description
Technical field
The invention belongs to polyurethane elastomer preparation technical fields, and in particular to environmentally friendly low hardness polyurethane elastic body
Preparation method.
Technical background
Polyurethane is mainly made of the macromolecular chain of carbamate repeating unit.It can be mainly divided by product form
Elastomer, soft bubble, hard bubble, fiber and adhesive etc..The hardness adjustable extent of polyurethane elastomer material is wider, can be from low hard
Degree A0 is adjusted to high rigidity D90.Currently, the low hardness polyurethane elastic body market demand is larger, be widely used in footwear material,
The industries such as rubber roller, printing, sport and medical instrument (Zhang Yijun, the application of low hardness polyurethane elastic body and progress,
Chemical industry and engineering technology).
The low hardness polyurethane elastic body prepared in patent CN103694440A and CN103408719A has good
Mechanical property, but all the adjacent benzene class plasticizer containing larger proportion, this micromolecular plasticizer often have migration, are easy
(Zhang Jing, the harm of phthalic ester plasticizer and regulatory status, modern chemical industry) is damaged to environmental and human health impacts,
Meanwhile after the migration of plasticizer to material surface, the hardness of material also can substantial increase, influence the long-term of product quality
Stability.Patent CN101781454A discloses a kind of low hardness polyurethane elastic body composite, passes through the composition
's
Mixing is poured the polyurethane elastomer of available soft, but poly- because there are also the propylene oxide of more ratio in system
Ether
Polyalcohol is only used for the not high application neck of intensity requirement so that the elastomer intensity of this method preparation substantially reduces
Domain.
Based on the problems in current low hardness polyurethane elastic body development process, the invention proposes a kind of not plasticizer-containings
Environment-friendly type low hardness polyurethane elastic body, excellent in mechanical performance, hardness is adjustable in a wider range, efficiently solves routine
It is low
The migration of plasticizer and the bad problem of mechanical property in durometric polyurethane elastomeric material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of low hardness polyurethane elastic body material, the material is without containing small
Molecule plasticizer has good mechanical property and environmental-protecting performance.It can be with fields such as footwear material, rubber roller, printing, medical instruments.
Low hardness polyurethane elastic body material in the present invention is made of the raw material of following parts by weight:
100 parts of polyalcohol
5-50 parts of isocyanates
0-20 parts of chain extender
1-20 parts of dissaving polymer
0-10 parts of catalyst
0-10 parts of antioxidant
0-10 parts of anti-UV agent
The polyalcohol includes molecular weight 300-8000, the polyester polyol of degree of functionality 2-4, polyether polyol, polyolefin
It is more
First alcohol, polyacrylate polyol, copolymerization ethoxylated polyhydric alcohol, castor oil polyhydric alcohol, palm oil polyalcohol, soybean oil are polynary
One or more of alcohol mixture.
The isocyanates includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, liquefied mdi, six methylenes
Group diisocyanate, dicyclohexyl methyl hydride diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, 1,4- hexamethylene two
Isocyanates, benzene dimethylene diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, six methylene of trimethyl -1,6-
Base
Diisocyanate, dimethyl diphenyl diisocyanate, Methylcyclohexyl diisocyanate, dimethyl diphenylmethane two are different
One or more of cyanate, dimethyl diphenylmethane diisocyanate, lysine diisocyanate mixture.
The chain extender includes 3,3 '-two chloro- 4,4 ' diphenylmethanediamiands, 3,5- dimethythiotoluene diamine, 3,
5- diethyl toluene diamine, ethylene glycol, butanediol, diglycol, propylene glycol, neopentyl glycol, methyl propanediol, oneself two
Alcohol,
Glycerin, glycerol, trihydroxy ethane, pentaerythrite, hydroquinone vinyl ethers, resorcinol vinyl ethers,
One of or a variety of mixture of the chain extenders such as bisphenol-A dihydroxyethyl ether, bisphenol-A dihydroxypropyl ether.
The dissaving polymer includes polyester-type, polyether-type, the polyamide of terminal hydroxy group and Amino End Group quantity 0-1000
One or more of type, polystyrene support type, polyfluorene type, polyimides ester type dissaving polymer copolymer and mixing
Object.
The catalyst includes that amines catalyst, bridged piperazine derivatives catalyst, morpholine class catalyst, imdazole derivatives are urged
Agent, organotin catalysts, carboxylic acid potassium class catalyst, organozinc catalyst, organic bismuth catalyst, titanate ester catalyst etc. are urged
One or more of agent compound.
The antioxidant includes antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant
1098, antioxidant 1135, antioxidant 1330, antioxidant 3114, antioxidant 1024, antioxidant 5057 etc. are one such
Or a variety of compounds.
The anti-UV agent includes ultraviolet absorbing agent UV-1, ultraviolet absorbing agent UV-320, ultraviolet absorbing agent
UV-326, ultraviolet absorbing agent UV-327, ultraviolet absorbing agent UV-328, ultraviolet absorbing agent UV-571, ultraviolet radiation absorption
Agent UV-1130 etc. is one such or a variety of compounds.
A kind of preparation method of environmental protection low hardness polyurethane elastic body, the described method comprises the following steps:
(3) prepared by performed polymer
By polynary dehydration of alcohols to moisture less than 0.03%, isocyanates is added, is reacted at 30-100 DEG C of reaction temperature of control
0.5-5 hours, obtain performed polymer.
(4) preparation of low hardness polyurethane elastic body
By above-mentioned performed polymer and metering chain extender, dissaving polymer, antioxidant, anti-UV agent, catalyst mixing is
It is even, it pours into the mold of certain temperature, arrives low hardness polyurethane elastic body after sulfidization molding.
It is an advantage of the invention that preparing the low hardness polyurethane bullet of good mechanical performance in the case where not containing plasticizer
Property body, behaviour
Make simply, nontoxic and pollution-free, product hardness stabilization, without small molecule of moving out, hardness does not change over time and changes.Environmental protection
While have both good mechanical property, durometer elastomer can be applied to more places and field.
Specific embodiment
The present invention will be further described for son with reference to embodiments, but the scope of the present invention is not limited to the embodiment party
Formula.
Embodiment 1
100 parts of polyester polyol PEA-2000
10-20 parts of toluene di-isocyanate(TDI) TDI-100
3,3 '-two 2-10 parts of chloro- 4,4 ' diphenylmethanediamiands
6-9 parts of polyester-type Hyperbranched Polymer with Terminal Hydroxyl
0.01-0.1 parts of organozinc catalyst
245 0.1-0.5 parts of antioxidant
0.1-0.5 parts of ultraviolet absorbing agent UV-1
Polyester polyol PEA-2000 is dehydrated to moisture less than 0.03%, TDI-100 is added, controls reaction temperature 60-
At 80 DEG C
Reaction 1-5 hours, obtains performed polymer.By this performed polymer and metering chain extender, dissaving polymer, antioxidant, anti-UV
Agent, catalyst are uniformly mixed, pour into 80-120 DEG C of mold, to get elastic to low hardness polyurethane after sulfidization molding
Body.
Embodiment 2
100 parts of polyester polyol PDA-2000
10-20 parts of toluene di-isocyanate(TDI) TDI-100
2-10 parts of 3,5- dimethythiotoluene diamine
10-15 parts of polyester-type Hyperbranched Polymer with Terminal Hydroxyl.
Claims (8)
1. a kind of preparation method of environmental protection low hardness polyurethane elastic body, it is characterised in that steps are as follows:
(1) prepared by performed polymer
By polynary dehydration of alcohols to moisture less than 0.03%, isocyanates is added, is reacted at 30-100 DEG C of reaction temperature of control
0.5-5 hours, obtain performed polymer；
(2) preparation of polyurethane elastomer
By above-mentioned performed polymer and metering chain extender, dissaving polymer, antioxidant, anti-UV agent, catalyst mixing is
It is even, it pours into the mold of certain temperature, arrives low hardness polyurethane elastic body after sulfidization molding；
The weight content of each raw material is as follows in above-mentioned preparation process:
100 parts of polyalcohol
5-50 parts of isocyanates
0-20 parts of chain extender
1-20 parts of dissaving polymer
0-10 parts of catalyst
0-10 parts of antioxidant
0-10 parts of anti-UV agent.
2. the environmentally friendly low hardness polyurethane elastic body according to claim 1, it is characterised in that the polyalcohol includes
Molecular weight
300-8000, the polyester polyol of degree of functionality 2-4, polyether polyol, polyolefin polyhydric alcohol, polyacrylate are polynary
Alcohol,
It is copolymerized ethoxylated polyhydric alcohol, castor oil polyhydric alcohol, palm oil polyalcohol, the mixing of one or more of soybean oil polyol
Object.
3. the environmentally friendly low hardness polyurethane elastic body according to claim 1, it is characterised in that the isocyanates packet
Include toluene
Diisocyanate, methyl diphenylene diisocyanate, liquefied mdi, hexamethylene diisocyanate, dicyclohexyl methyl hydride
Diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, 1,4- cyclohexane diisocyanate, phenylenedimethylidyne two
Isocyanates, cyclohexanedimethyleterephthalate diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, dimethyl connection
Benzene
Diisocyanate, Methylcyclohexyl diisocyanate, dimethyl diphenylmethane diisocyanate, dimethyl diphenyl first
One or more of alkane diisocyanate, lysine diisocyanate mixture.
4. the environmentally friendly low hardness polyurethane elastic body according to claim 1, it is characterised in that the chain extender includes
3,3’-
Two chloro- 4,4 ' diphenylmethanediamiands, 3,5- dimethythiotoluene diamine, 3,5- diethyl toluene diamine, ethylene glycol, fourth
Two
Alcohol, diglycol, propylene glycol, neopentyl glycol, methyl propanediol, hexylene glycol, Glycerin, glycerol, three
It is hydroxyl ethane, pentaerythrite, hydroquinone vinyl ethers, resorcinol vinyl ethers, bisphenol-A dihydroxyethyl ether, double
One of or a variety of mixture of the chain extenders such as phenol A dihydroxypropyl ether.
5. the environmentally friendly low hardness polyurethane elastic body according to claim 1, it is characterised in that the dissaving polymer
Including end
The polyester-type of hydroxyl and Amino End Group quantity 0-1000, polyamide, polystyrene support type, polyfluorene type, gather polyether-type
One or more of acid imide ester type dissaving polymer copolymer and mixture.
6. the environmentally friendly low hardness polyurethane elastic body according to claim 1, it is characterised in that the catalyst includes
Amine is urged
Agent, bridged piperazine derivatives catalyst, morpholine class catalyst, imdazole derivatives catalyst, organotin catalysts, carboxylic acid potassium
One or more of catalyst such as class catalyst, organozinc catalyst, organic bismuth catalyst, titanate ester catalyst
Compound.
7. the environmentally friendly low hardness polyurethane elastic body according to claim 1, it is characterised in that the antioxidant includes
Antioxidant
245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098, antioxidant 1135, antioxidant
1330, one such or a variety of compound such as antioxidant 3114, antioxidant 1024, antioxidant 5057.
8. the environmentally friendly low hardness polyurethane elastic body according to claim 1, it is characterised in that the anti-UV agent includes
Ultraviolet absorbing agent UV-1, ultraviolet absorbing agent UV-320, ultraviolet absorbent uv-326, ultraviolet absorbing agent UV-
327, ultraviolet absorbing agent UV-328, ultraviolet absorbing agent UV-571, ultraviolet absorbing agent UV-1130 etc. are one such
Or
A variety of compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711448439.0A CN109970946A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of environmental protection low hardness polyurethane elastic body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711448439.0A CN109970946A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of environmental protection low hardness polyurethane elastic body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109970946A true CN109970946A (en) | 2019-07-05 |
Family
ID=67072075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711448439.0A Pending CN109970946A (en) | 2017-12-27 | 2017-12-27 | A kind of preparation method of environmental protection low hardness polyurethane elastic body |
Country Status (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484120A (en) * | 2019-08-26 | 2019-11-22 | 东莞市兴茂橡塑科技有限公司 | A kind of bi-component glaze layered material and its preparation method and application |
| CN114075383A (en) * | 2020-08-12 | 2022-02-22 | 苏州怒鲨智能科技有限公司 | High-strength flexible sensor material and preparation method thereof |
| CN114316198A (en) * | 2022-01-18 | 2022-04-12 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Vibration-damping polyurethane elastomer material for rail transit and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110484120A (en) * | 2019-08-26 | 2019-11-22 | 东莞市兴茂橡塑科技有限公司 | A kind of bi-component glaze layered material and its preparation method and application |
| CN110484120B (en) * | 2019-08-26 | 2021-06-11 | 东莞市兴茂橡塑科技有限公司 | Bi-component glaze layer material and preparation method and application thereof |
| CN114075383A (en) * | 2020-08-12 | 2022-02-22 | 苏州怒鲨智能科技有限公司 | High-strength flexible sensor material and preparation method thereof |
| CN114316198A (en) * | 2022-01-18 | 2022-04-12 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Vibration-damping polyurethane elastomer material for rail transit and preparation method thereof |
| CN114316198B (en) * | 2022-01-18 | 2023-09-15 | 中国铁道科学研究院集团有限公司金属及化学研究所 | Vibration reduction polyurethane elastomer material for rail transit and preparation method thereof |
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