CN106674474A - Polyurethane shoe material capable of demoulding quickly at room temperature, and preparation method of polyurethane shoe material - Google Patents
Polyurethane shoe material capable of demoulding quickly at room temperature, and preparation method of polyurethane shoe material Download PDFInfo
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- CN106674474A CN106674474A CN201611270460.1A CN201611270460A CN106674474A CN 106674474 A CN106674474 A CN 106674474A CN 201611270460 A CN201611270460 A CN 201611270460A CN 106674474 A CN106674474 A CN 106674474A
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- shoe material
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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
- C08G18/6666—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
- C08G18/6688—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 C08G18/3271
-
- 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
- C08G18/08—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
-
- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- 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
-
- 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
- C08G18/7657—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
-
- 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
- C08G2410/00—Soles
Landscapes
- 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 invention relates to a polyurethane shoe material capable of demoulding quickly at room temperature, and a preparation method of the polyurethane shoe material, and belongs to the technical field of polyurethane application. The polyurethane shoe material adopts a double-component system, wherein a polymer component is prepared by mixing a chain extender triethanolamine, 2-functionality-degree and 3-functionality-degree polyether polyol and anti-yellowing agent, and an environment-friendly catalyst ; a prepolymer component is prepared by performing a reaction on MDI (methylene diphenyl diisocyanate) modified by methylene diphenyl diisocyanate and carbodiimide, polyether polyol and a plasticizer. The two components are quickly mixed to obtain a polyurethane elastomer. The polyurethane shoe material is mainly applied to manufacturing of environment-friendly high-toughness transparent low-hardness products which requires room-temperature operation and can demould quickly at room temperature and is chiefly used for manufacturing shoe-pad and the like.
Description
Technical field
The present invention relates to a kind of polyurethane shoe material of room temperature fast demoulding and preparation method thereof, belong to polyurethane application skill
Art field.
Background technology
Polyurethane is a kind of high molecular synthetic material of performance between rubber and plastics, is characterized in that hardness adjusts model
Width is enclosed, the elasticity of existing rubber has the hardness of plastics again, with good mechanical performance, anti-wear performance and rebound performance.Wherein,
Polyurethane footwear material is a kind of material of soft, it is desirable to which hardness is low, and resilience is good, and surface is micro- viscous.This kind of general material is required for
90~120 DEG C of shaping curings of high temperature, can just accomplish to mold for 1-2 minutes.
The content of the invention
The technical problems to be solved by the invention are to provide polyurethane shoe material and its preparation of a kind of room temperature fast demoulding
Method, the polyurethane shoe material hardness is low, and between double O 40~60, normal-temperature operation good fluidity, toughness of products is good, mould
Without heating, normal temperature 1 '~1 ' 30 " can mold, production efficiency is high.
A kind of polyurethane shoe material of room temperature fast demoulding, including two kinds of components：
(1) polymers compositions：It is made up of the raw material by following percent by weight：Chain extender 1%~3%, degree of functionality is
2nd, PPOX PPG 20%~30% of the number-average molecular weight in the range of 2000~4000, degree of functionality is that 3, number is equal
PPOX PPG 65.85%~77.6% of the molecular weight in the range of 5000~6000, antioxidant 0~1% resists
Ultra-violet absorber 0~1% and organo-metallic catalyst 0.15%~0.4%；
(2) pre-polymer component：It is made up of the raw material by following percent by weight：It is isocyanates 23.4%~37%, poly-
Ethoxylated polyhydric alcohol 63%~66.6% and plasticizer 0~10%, isocyano-content are 5%~10%.
Polymers compositions is 100 with the mass ratio of pre-polymer component:30~35.
The PPOX ethoxylated polyhydric alcohol from PPG500, PPG2000, PPG3000, PPG4000, PPG28,
One or more in PPG3050, PPG330N and PPG3600, preferably PPG2000 and PPG330N, PPG3600；Chain extension
Small molecular alcohol TEA is selected in agent.
Antioxidant refers to 1076 (β-positive octadecanol ester of (4- hydroxy phenyl -3,5- di-t-butyls) propionic acid) or antioxidant
One or two mixture in 1010 (four (β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol esters)；It is purple
Ultraviolet absorbers are selected from UV328 (2- (the tertiary amyl phenyl of 2'- hydroxyls -3', 5'- bis-) BTA) or UV329 (2- (2'- hydroxyls
Base -5'- spies octyl phenyl) BTA) one or two mixture.
The organo-metallic catalyst is organo-bismuth or organic zinc environmental protection catalyst.
The isocyanates is selected from MDI, liquefied mdi (MDI of Carbodiimide-Modified) and its mixture.
The PPG refers to more than the one or two kinds of in PPG2000, PPG3000, PPG3050.
The preparation method of the polyurethane shoe material of the fast demoulding, will polymers compositions mix with pre-polymer component,
After stirring, pour into mould, cold curing, the demoulding obtains low hardness polyurethane bullet of the hardness between double O 55~60
Gonosome.
The mixing temperature between 25~35 DEG C, hardening time is 40 "~1 ', 1 '~1.5 ' demouldings.
Polymers compositions is prepared as follows method and obtains：By each raw material in 100~110 DEG C, dehydrated under vacuum to moisture
Less than 0.05%；Pre-polymer component is prepared as follows method and obtains：Each raw material is reacted 2~3 hours at 70 DEG C~90 DEG C.
Wherein, polymers compositions is individually packed with pre-polymer component, is remixed during for production of articles, and appellation of the present invention
Polymers compositions, pre-polymer component are intended merely to the convenience in statement.
The present invention uses bicomponent system, and polymers compositions is by chain extender triethanolamine, 2 degrees of functionality, 3 degrees of functionality
PPG and anti-yellowing agent, environmental protection catalyst are mixed to prepare, pre-polymer component be by methyl diphenylene diisocyanate and
The MDI of Carbodiimide-Modified is obtained with PPG and plasticizer reaction.Two components are quickly mixed to get elastic polyurethane
Body, present invention is mainly used for normal-temperature operation is required, is capable of the environmental protection of normal temperature fast demoulding, the transparent soft product of good toughness
Make, be used for making shoe-pad etc..
Specific embodiment
Embodiment material therefor：
Percentage in following examples refers both to mass percent.
Embodiment 1：
Polymers compositions：Triethanolamine 2%, degree of functionality 2, the PPG (PPG2000) 20% of molecular weight 2000, official
The PPG (PPG3600) 76.8% of energy degree 3, molecular weight 6000, organic bismuth catalyst 0.2%, antioxidant 0.5% is purple
Ultraviolet absorbers 0.5%, at 100~110 DEG C, are dehydrated to moisture less than 0.05% under -0.095MPa, obtain polymers compositions.
Pre-polymer component：The PPG PPG3000 66.6% of degree of functionality 2, molecular weight 3000, MDI 11.7%, liquid
Change MDI 11.7%, DOTP 10% obtains isocyanide in 70 DEG C~90 DEG C small vacuum (- 0.095MPa) the removing bubbles of reaction 2~3
Acid group content is 5.5% prepolymer.
By the temperature control of polymers compositions and pre-polymer component at 25~35 DEG C, according to 100：35 mass ratio is mixed
Close, after quickly stirring, in pouring into ready mould already, cold curing, hardening time is 50, and " left and right takes off for 1 minute
Mould, obtains the polyurethane elastomer of double O 55.
Embodiment 2：
Polymers compositions：Triethanolamine 3%, degree of functionality 2, the PPG (PPG28) 30% of molecular weight 4000, function
The degree 3, PPG (PPG330N) 65.85% of molecular weight 5000, organic bismuth catalyst 0.15%, antioxidant 0.5% is purple
Ultraviolet absorbers 0.5%, at 100~110 DEG C, are dehydrated to moisture less than 0.05% under -0.095MPa, obtain polymers compositions.
Pre-polymer component：PPG (PPG2000) 66.6%, MDI 13.4% of degree of functionality 2, molecular weight 2000,
Liquefied mdi 20%, reacts 2~3 hours at 70 DEG C~90 DEG C, vacuum (- 0.095MPa) removing bubble, obtains isocyano and contains
Measure the prepolymer for 7.5%.
By the temperature control of polymers compositions and pre-polymer component at 25~35 DEG C, according to 100：30 ratio mixing, soon
After speed stirs, in pouring into ready mould already, cold curing, hardening time is 40, and " left and right, 1 ' 10 " demoulding is obtained
To the soft urethane elastomeric material of double O60.
Embodiment 3：
Polymers compositions：Triethanolamine 1%, degree of functionality 2, the PPG (PPG2000) 20% of molecular weight 2000, official
The PPG (PPG330N) 77.6% of energy degree 3, molecular weight 5000, organic bismuth catalyst 0.3%, organic zinc 0.1% resists
Oxygen agent 0.5%, ultra-violet absorber 0.5%, at 100~110 DEG C, is dehydrated to moisture less than 0.05% under -0.095MPa, obtains
Polymers compositions.
Pre-polymer component：The PPG (PPG3050) 19% of degree of functionality 3, molecular weight 3000, degree of functionality 2, molecular weight
2000 PPG (PPG2000) 44%, MDI 11%, liquefied mdi 26% reacts 2~3 hours at 70 DEG C~90 DEG C,
Vacuum (- 0.095MPa) removes bubble, obtains the prepolymer that isocyano-content is 8.5%.
By the temperature control of polymers compositions and pre-polymer component at 25~35 DEG C, according to 100：30 mass ratio is mixed
Close, after stirring, in pouring into ready mould already, cold curing, hardening time is 40 "~1 ' left and right, 1 '~1 '
30 " can the demoulding, obtain the low hardness polyurethane elastic body material of double O55~60.
Comparison example 4：
Polymers compositions：The PPG (PPG500) 3% of degree of functionality 3, molecular weight 500, degree of functionality 3, molecular weight
6000 PPG (PPG3600) 95.6%, antioxidant 0.5%, ultra-violet absorber 0.5% has bismuth class catalyst
0.3%, organozinc catalyst 0.1% is dehydrated to moisture less than 0.05% under 100~110 DEG C, -0.095MPa, is polymerized
Thing component.
Pre-polymer component：The PPG (PPG3050) 33% of 3 degrees of functionality, molecular weight 3000, degree of functionality 2, molecular weight
3000 PPG (PPG3000) 33%, pure MDI 10%, liquefied mdi 24% is small in 70 DEG C~90 DEG C reactions 2~3
When, vacuum (- 0.095MPa) removing bubble obtains the prepolymer that isocyano-content is 8.0%.
By the temperature control of polymers compositions and pre-polymer component at 25~35 DEG C, according to 100：21 mass ratio is mixed
Close, after stirring, pour into ready mould already, cold curing, hardening time, at 1 minute or so, takes off for 3-4 minutes
Mould, obtains the transparent polyurethane elastomer material of double O 60.
The test data such as following table of room temperature fast demoulding polyurethane shoe material：
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparison example 4 |
| Hardness (double O) | 55 | 58 | 60 | 60 |
| The transparency | It is transparent | It is transparent | It is transparent | It is transparent |
| Gel time | 50″ | 40″ | 1′ | 1′ |
| Open time | 1′ | 1′10″ | 1′30″ | 4′ |
| Toughness | It is excellent | It is excellent | It is excellent | It is excellent |
Claims (9)
1. a kind of polyurethane shoe material of room temperature fast demoulding, it is characterised in that including two kinds of components：
(1) polymers compositions：It is made up of the raw material by following percent by weight：Chain extender 1%~3%, degree of functionality is 2, number
PPOX PPG 20%~30% of the average molecular weight in the range of 2000~4000, degree of functionality is 3, the equal molecule of number
Measure the PPOX PPG 65.85%~77.6% in the range of 5000~6000, antioxidant 0~1%, uvioresistant
Light absorbers 0~1% and organo-metallic catalyst 0.15%~0.4%；
(2) pre-polymer component：It is made up of the raw material by following percent by weight：Isocyanates 23.4%~37%, polyethers is more
First alcohol 63%~66.6% and plasticizer 0~10%, isocyano-content are 5%~10%.
2. a kind of polyurethane shoe material of room temperature fast demoulding according to claim 1, it is characterised in that polymers compositions
It is 100 with the mass ratio of pre-polymer component:30~35.
3. a kind of polyurethane shoe material of room temperature fast demoulding according to claim 1, it is characterised in that the polycyclic oxygen
Propane ethoxylated polyhydric alcohol selects PPG500, PPG2000, PPG3000, PPG4000, PPG28, PPG3050, PPG330N and PPG3600
In one or more；Chain extender selects small molecular alcohol TEA.
4. the polyurethane shoe material of a kind of room temperature fast demoulding according to claim 1, it is characterised in that antioxidant refers to
1076 or antioxidant 1010 in one or two mixture；Ultra-violet absorber be selected from UV328 or UV329 one or two
Mixture.
5. a kind of polyurethane shoe material of room temperature fast demoulding according to claim 1, it is characterised in that organic gold
Metal catalyst is organo-bismuth or organic zinc environmental protection catalyst.
6. a kind of polyurethane shoe material of room temperature fast demoulding according to claim 1, it is characterised in that the isocyanic acid
Ester is selected from MDI, liquefied mdi and its mixture.
7. as described in claim 1-7 any one the polyurethane shoe material of room temperature fast demoulding preparation method, its feature exists
In, polymers compositions is mixed with pre-polymer component, after stirring, pour into mould, cold curing, the demoulding obtains hardness
Low hardness polyurethane elastic body between double O55~60.
8. the preparation method of the polyurethane shoe material of room temperature fast demoulding according to claim 8, it is characterised in that described mixed
Close temperature between 25~35 DEG C, "~1 ', 1 '~1.5 ' demouldings that hardening time is 40.
9. according to claim 7 or 8 the polyurethane shoe material of room temperature fast demoulding preparation method, it is characterised in that it is poly-
Polymer component is prepared as follows method and obtains：Each raw material is less than 0.05% in 100~110 DEG C, dehydrated under vacuum to moisture；
Pre-polymer component is prepared as follows method and obtains：Each raw material is reacted 2~3 hours at 70 DEG C~90 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611270460.1A CN106674474A (en) | 2016-12-30 | 2016-12-30 | Polyurethane shoe material capable of demoulding quickly at room temperature, and preparation method of polyurethane shoe material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611270460.1A CN106674474A (en) | 2016-12-30 | 2016-12-30 | Polyurethane shoe material capable of demoulding quickly at room temperature, and preparation method of polyurethane shoe material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108503790A (en) * | 2018-03-09 | 2018-09-07 | 旭川化学（昆山）有限公司 | A kind of dual-component polyurethane mold glue and preparation method thereof |
| CN109912760A (en) * | 2017-12-13 | 2019-06-21 | 上海优迈材料科技有限公司 | A kind of oil-resisting type floor-cleaning machine water suction adhesive tape and preparation method thereof |
| CN110903457A (en) * | 2019-12-12 | 2020-03-24 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for manufacturing rapid demoulding high-temperature-resistant transparent model material and preparation method thereof |
| CN112778491A (en) * | 2020-12-30 | 2021-05-11 | 山东一诺威聚氨酯股份有限公司 | High-transparency rapid-mold-opening polyurethane elastomer and preparation method thereof |
| CN114456347A (en) * | 2022-02-28 | 2022-05-10 | 赢聚化学技术研发(南京)有限公司 | Preparation method of anti-slip polyurethane sole transparent sole attaching material |
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| CN103833951A (en) * | 2014-03-24 | 2014-06-04 | 山东一诺威聚氨酯股份有限公司 | Preparation method of quick-demoulding low-hardness polyurethane elastomer composite |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912760A (en) * | 2017-12-13 | 2019-06-21 | 上海优迈材料科技有限公司 | A kind of oil-resisting type floor-cleaning machine water suction adhesive tape and preparation method thereof |
| CN108503790A (en) * | 2018-03-09 | 2018-09-07 | 旭川化学（昆山）有限公司 | A kind of dual-component polyurethane mold glue and preparation method thereof |
| CN110903457A (en) * | 2019-12-12 | 2020-03-24 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for manufacturing rapid demoulding high-temperature-resistant transparent model material and preparation method thereof |
| WO2021114664A1 (en) * | 2019-12-12 | 2021-06-17 | 山东一诺威聚氨酯股份有限公司 | Polyurethane elastomer for manufacturing quick-demolding high temperature-resistant transparent model material and preparation method therefor |
| CN112778491A (en) * | 2020-12-30 | 2021-05-11 | 山东一诺威聚氨酯股份有限公司 | High-transparency rapid-mold-opening polyurethane elastomer and preparation method thereof |
| CN114456347A (en) * | 2022-02-28 | 2022-05-10 | 赢聚化学技术研发(南京)有限公司 | Preparation method of anti-slip polyurethane sole transparent sole attaching material |
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Application publication date: 20170517 |