CN104448791A - High-rigidity transparent polyurethane elastomer and preparation method thereof - Google Patents
High-rigidity transparent polyurethane elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of polyurethane elastomer, and particularly relates to a high-rigidity transparent polyurethane elastomer and a preparation method thereof. The high-rigidity transparent polyurethane elastomer is prepared from a polymer component and an isocyanic acid component, wherein the polymer component comprises the following raw materials: polypropylene oxide polyether polyol with the functionality of 3 and the number-average molecular weight of 400-5000, polypropylene oxide polyether polyol with the functionality of 4 and the number-average molecular weight of 300-600, an antioxidant, an ultraviolet absorbent and an organo-metallic catalyst; the prepolymer component comprises the following raw materials: isocyanate, polyether polyol and a plasticizer. The high-rigidity transparent polyurethane elastomer provided by the invention has the advantages of high transparency and product stability, is various in esthetic effect, very rigid in texture and suitable for making certain products capable of substituting epoxy, can achieve the rigidity and transparency of epoxy resin and has yellowing resistance and toughness which are unparalleled by those of the epoxy. The preparation method provided by the invention has the advantages of reasonable process and easy to industrially produce.
Description
Technical field
The invention belongs to polyurethane elastomer field, be specifically related to a kind of high-hard, transparent polyurethane elastomer and preparation method thereof.
Background technology
Urethane is the high molecular synthetic material of a kind of performance between rubber and plastics, is characterized in that hardness setting range is wide, and the elasticity of existing rubber has again the hardness of plastics, has good mechanical property, wear resisting property and rebound performance.Along with the development of urethane cause, the purposes of polyurethane products is also more and more extensive, also more and more higher to the performance requriements of product.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of high-hard, transparent polyurethane elastomer, there is diversified aesthetic effect, and quality very hard, have higher yellowing resistance and toughness, the present invention also provides its preparation method, rational technology, is easy to suitability for industrialized production.
High-hard, transparent polyurethane elastomer of the present invention, be made up of polymeric components and isocyano component:
Polymeric components is made up of the raw material of following weight percentage:
The poly(propylene oxide) polyether glycol 40% ~ 91.85% that functionality is 3, number-average molecular weight is 400 ~ 5000,
Functionality is 4, and number-average molecular weight is the poly(propylene oxide) polyether glycol 5% ~ 59.6% of 300 ~ 600,
Oxidation inhibitor 0.3% ~ 1%,
Ultraviolet-resistant absorbent 0.2 ~ 0.6%,
Organo-metallic catalyst 0.15% ~ 0.4%;
Prepolymer component is made up of the raw material of following weight percentage:
Isocyanic ester 65% ~ 73%, polyether glycol 22% ~ 35% and softening agent 1% ~ 5%.
Wherein:
The poly(propylene oxide) polyether glycol that functionality is 3, number-average molecular weight is 400 ~ 5000 is one or more in PPG400, PPG330N or PPG500; Preferred PPG500.
The poly(propylene oxide) polyether glycol that functionality is 4, number-average molecular weight is 300 ~ 600 is one or both in PPG430 or PPG600; Preferred PPG430.
Oxidation inhibitor is antioxidant 1076 (β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid) or antioxidant 1010 (four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester) in one or both.Oxidation inhibitor is 0.3 ~ 1%, preferably 0.5%.
Ultraviolet-resistant absorbent is UV328 (2-(2'-hydroxyl-3', 5'-bis-tertiary amyl phenyl) benzotriazole) or UV329 (2-(2'-hydroxyl-5'-special octyl phenyl) benzotriazole) in one or both.Ultraviolet-resistant absorbent is 0.2 ~ 0.6%, preferably 0.5%.
Catalyzer is organic bismuth catalyst, organozinc catalyst or zinc bismuth composite metal catalyst one wherein.Zinc bismuth composite metal catalyst is that organic bismuth catalyst and organozinc catalyst are mixed to get with arbitrary proportion.The preferred bi content of organic bismuth catalyst is the organic bismuth catalyst of 16% or 18%.Catalyzer is common commercial products.
Isocyanic ester is one or both in liquefied mdi or MDI-50.
Vulcabond is IPDI or H
12one or both in MDI.
Polyether glycol is one or more in PPG500, PPG2000 or PPG3050, preferred PPG3050.
Softening agent is one or both in DOTP, TXIB or DOP.Softening agent is 1 ~ 10%, preferably 5%.
Appellation polymeric components of the present invention, the prepolymer component convenience just in order to state.
High-hard, transparent method for preparing polyurethane elastic body of the present invention, comprises the following steps:
(1) polymeric components preparation
By all raw material mixing of polymeric components, at 100 ~ 110 DEG C, dewater under-0.095MPa to moisture and be less than 0.05%, obtain polymeric constituent;
(2) prepolymer component preparation
In massfraction, by all raw material mixing of prepolymer component, 70 DEG C ~ 90 DEG C reactions 2 ~ 3 hours, obtain the prepolymer that isocyano-content is 19% ~ 19.5%.
Wherein:
Polymeric components and prepolymer component are packed separately, during for production of articles, polymeric components is mixed according to the ratio that mass ratio is 100:150 or 100:100 with prepolymer component, mixing temperature is 25 ~ 35 DEG C, after stirring, and pours in mould, self-vulcanizing, set time, the demoulding, obtained transparent polyurethane elastomer at 8-10 minute.Demould time is 15 ~ 20 minutes.
High-hard, transparent polyurethane elastomer of the present invention, is mainly used in replacing epoxy resin, makes the high transparent material requiring environmental protection, good toughness, is used for making joint sealant, nameplate, artwork etc.
In sum, the present invention has the following advantages:
(1) high-hard, transparent polyurethane elastomer transparency of the present invention is high, product is stablized, this polyurethane elastomer not only has diversified aesthetic effect, and quality very hard, be applicable to doing some products replacing epoxy, hardness and the transparency of epoxy resin can be reached, there is again the incomparable yellowing resistance of epoxy and toughness.
(2) the invention provides its preparation method, rational technology, be easy to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Following examples, are not specifically noted, and percentage ratio all refers to mass percent.
In embodiment, all raw materials are except specified otherwise, are commercial.
Embodiment material therefor:
PPG500 number-average molecular weight 500, polyoxypropylene trivalent alcohol
PPG600 number-average molecular weight 600, polyoxypropylene tetravalent alcohol
PPG400 number-average molecular weight 400, polyoxypropylene trivalent alcohol
PPG430 number-average molecular weight 300, polyoxypropylene tetravalent alcohol
PPG2000 number-average molecular weight 2000, polyoxypropylene dibasic alcohol
PPG330N number-average molecular weight 5000, proportion of primary OH groups 75%, polyoxypropylene trivalent alcohol
PPG3600 number-average molecular weight 5000, proportion of primary OH groups 75%, polyoxypropylene trivalent alcohol
PPG3050 number-average molecular weight 3000 polyoxypropylene trivalent alcohol
The MDI of liquefied mdi Carbodiimide-Modified
MDI-50 4,4 '-diphenylmethanediisocyanate 50% and 2,4 '-diphenylmethanediisocyanate 50%
IPDI isoflurane chalcone diisocyanate
H12MDI hydrogenated diphenyl methane diisocyanate;
DOTP dioctyl terephthalate
TXIB 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate.
Embodiment 1
Polymeric components: the polyether glycol (PPG430) 5% of functionality 4, molecular weight 300, the polyether glycol (PPG400) 79% of functionality 3, molecular weight 400, the polyether glycol (PPG330N) 14.8% of functionality 3, molecular weight 5000, organic bismuth catalyst 0.2%, antioxidant 1010 0.5%, UV light absorber UV329 0.5%, at 100 DEG C, dewater under-0.095MPa to moisture and be less than 0.05%, obtain polymeric constituent.
Prepolymer component: be with the polyether glycol (PPG3050) 10.5% of polyether glycol (PPG2000) 24.5%, the 3 functionality molecular weight 3000 of 2 functionality molecular weight 2000, MDI-50 32.5%, liquefied mdi 32.5%, remove bubble 80 DEG C of reaction 2.5 little vacuum (-0.095MPa), obtain the prepolymer that isocyano-content is 19%.
The temperature of polymeric components and prepolymer component is controlled at 30 DEG C, mixes, after stirring according to the mass ratio of 100:150, pour into already in ready mould, self-vulcanizing, set time was at 10 minutes, the demoulding in 18 minutes, obtains the high transparency polyurethane elastomer of shore 75D.
Embodiment 2:
Polymeric components: the polyether glycol (PPG500) 91.85% of functionality 3, molecular weight 500, the polyether glycol (430) 7% of functionality 4, molecular weight 300, organozinc catalyst 0.15%, antioxidant 1076 0.5%, UV light absorber UV3280.5%, at 105 DEG C, dewater under-0.095MPa to moisture and be less than 0.05%, obtain polymeric constituent.
Prepolymer component: the polyether glycol (PPG3050) 32.3% of 3 functionality molecular weight 3000, MDI-50 34.7%, liquefied mdi 33%, 70 DEG C of reactions 3 hours, vacuum (-0.095MPa) removes bubble, obtains the prepolymer that isocyano-content is 19%.
The temperature of polymeric components and prepolymer component is controlled at 35 DEG C, mixes, after stirring according to the ratio of 100:150, pour into already in ready mould, self-vulcanizing, set time was at 8 minutes, the demoulding in 20 minutes, obtains the high transparency polyurethane elastomer material of shore 80D.
Embodiment 3:
Polymeric components: the polyether glycol (PPG500) 90.85% of functionality 3, molecular weight 500, the polyether glycol (430) 8% of functionality 4, molecular weight 300, zinc bismuth composite catalyst (organic bismuth catalyst and organozinc catalyst mix with mass ratio 1:1) 0.15%, antioxidant 1076 0.5%, UV light absorber UV328 0.5%, at 110 DEG C, dewater under-0.095MPa to moisture and be less than 0.05%, obtain polymeric constituent.
Prepolymer component:
It is the polyether glycol (PPG3050) 11% with 3 functionality, molecular weight 3000, the polyether glycol (PPG500) 11% of functionality 3, molecular weight 500, MDI-5032%, liquefied mdi 41%, TXIB 5% was 90 DEG C of reactions 2 hours, vacuum (-0.095MPa) removes bubble, obtains the prepolymer that isocyano-content is 19.5%.
The temperature of polymeric components and prepolymer component is controlled at 25 DEG C, mix according to the mass ratio of 100:150, after stirring, pour into already in ready mould, self-vulcanizing, set time, 20 minutes can the demoulding at 10 minutes, obtains the high transparency polyurethane elastomer material of shore 85D.
Comparative example
Polymeric components: the polyether glycol (PPG400) 40% of functionality 3, molecular weight 400, the polyether glycol (PPG600) 59.6% of functionality 4, molecular weight 600, mercury catalyst catalyzer 0.4%, 100 ~ 110 DEG C, dewatering to moisture under-0.095MPa is less than 0.05%, obtains polymeric constituent.
Isocyano component: the DOTP of IPDI 85% and 15% is mixed to get isocyano-content 31% isocyano component.
The temperature of polymeric components and prepolymer component is controlled at 30 DEG C, mixes, after stirring according to the mass ratio of 100:100, pour into already in ready mould, self-vulcanizing, set time was at 5 minutes, the demoulding in 20 minutes, obtains the high transparency polyurethane elastomer material of shore 83D.
Product embodiment 1-3 and comparative example prepared carries out performance test, and test result is in table 1.
The performance test results of the product that table 1 embodiment 1-3 and comparative example prepare
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Hardness (Shao D) | 75D | 80D | 85D | 83D |
| The transparency | Transparent | Transparent | Transparent | Transparent |
| Toughness | Excellent | Excellent | Excellent | Well |
Claims (10)
1. a high-hard, transparent polyurethane elastomer, is characterized in that: be made up of polymeric components and isocyano component:
Polymeric components is made up of the raw material of following weight percentage:
The poly(propylene oxide) polyether glycol 40% ~ 91.85% that functionality is 3, number-average molecular weight is 400 ~ 5000,
Functionality is 4, and number-average molecular weight is the poly(propylene oxide) polyether glycol 5% ~ 59.6% of 300 ~ 600,
Oxidation inhibitor 0.3% ~ 1%,
Ultraviolet-resistant absorbent 0.2 ~ 0.6%,
Organo-metallic catalyst 0.15% ~ 0.4%;
Prepolymer component is made up of the raw material of following weight percentage:
Isocyanic ester 65% ~ 73%, polyether glycol 22% ~ 35% and softening agent 1% ~ 5%.
2. high-hard, transparent polyurethane elastomer according to claim 1, is characterized in that:
The poly(propylene oxide) polyether glycol that functionality is 3, number-average molecular weight is 400 ~ 5000 is one or more in PPG400, PPG330N or PPG500;
The poly(propylene oxide) polyether glycol that functionality is 4, number-average molecular weight is 300 ~ 600 is one or both in PPG430 or PPG600.
3. high-hard, transparent polyurethane elastomer according to claim 1, is characterized in that: oxidation inhibitor is one or both in antioxidant 1076 or antioxidant 1010; UV light absorber is one or both in UV328 or UV329.
4. high-hard, transparent polyurethane elastomer according to claim 1, is characterized in that: organic bismuth catalyst, organozinc catalyst or zinc bismuth composite metal catalyst one wherein.
5. high-hard, transparent polyurethane elastomer according to claim 1, is characterized in that: isocyanic ester is one or both in liquefied mdi or MDI-50.
6. high-hard, transparent polyurethane elastomer according to claim 1, is characterized in that: vulcabond is IPDI or H
12one or both in MDI.
7. high-hard, transparent polyurethane elastomer according to claim 1, is characterized in that: polyether glycol is one or more in PPG500, PPG2000 or PPG3050.
8. high-hard, transparent polyurethane elastomer according to claim 1, is characterized in that: softening agent is one or both in DOTP, TXIB or DOP.
9. the arbitrary described high-hard, transparent method for preparing polyurethane elastic body of claim 1-8, is characterized in that: comprise the following steps:
(1) polymeric components preparation
By all raw material mixing of polymeric components, dewater to moisture and be less than 0.05%, obtain polymeric constituent;
(2) prepolymer component preparation
In massfraction, by all raw material mixing of prepolymer component, 70 DEG C ~ 90 DEG C reactions 2 ~ 3 hours, obtain the prepolymer that isocyano-content is 19% ~ 19.5%.
10. high-hard, transparent method for preparing polyurethane elastic body according to claim 9, it is characterized in that: polymeric components and prepolymer component are packed separately, during for production of articles, polymeric components mixed according to the ratio that mass ratio is 100:150 or 100:100 with prepolymer component, mixing temperature is 25 ~ 35 DEG C, after stirring, pour in mould, self-vulcanizing, set time is at 8-10 minute, the demoulding, obtains transparent polyurethane elastomer.
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| CN104974323A (en) * | 2015-06-26 | 2015-10-14 | 广东元星工业新材料有限公司 | Production mould of concrete decoration material |
| CN105111404A (en) * | 2015-08-27 | 2015-12-02 | 厦门明睐科技有限公司 | Preparation method of polyurethane elastomer |
| CN105622882A (en) * | 2016-02-04 | 2016-06-01 | 福州美创美工艺品有限公司 | Light-permeable polyurethane artificial material manufacturing method and light-permeable polyurethane artificial material manufacturing composition |
| CN105801812A (en) * | 2016-04-07 | 2016-07-27 | 苏州绿朗新材料科技有限公司 | Polyurethane elastomer and preparation method thereof |
| CN107216437A (en) * | 2017-04-28 | 2017-09-29 | 上海鹤城高分子科技有限公司 | A kind of water white transparency polyurethane rotational forming model's material and preparation method thereof |
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| CN104974323A (en) * | 2015-06-26 | 2015-10-14 | 广东元星工业新材料有限公司 | Production mould of concrete decoration material |
| CN105111404A (en) * | 2015-08-27 | 2015-12-02 | 厦门明睐科技有限公司 | Preparation method of polyurethane elastomer |
| CN105622882A (en) * | 2016-02-04 | 2016-06-01 | 福州美创美工艺品有限公司 | Light-permeable polyurethane artificial material manufacturing method and light-permeable polyurethane artificial material manufacturing composition |
| CN105801812A (en) * | 2016-04-07 | 2016-07-27 | 苏州绿朗新材料科技有限公司 | Polyurethane elastomer and preparation method thereof |
| CN107216437A (en) * | 2017-04-28 | 2017-09-29 | 上海鹤城高分子科技有限公司 | A kind of water white transparency polyurethane rotational forming model's material and preparation method thereof |
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| 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 |
| CN109021195A (en) * | 2018-08-07 | 2018-12-18 | 山东诺威聚氨酯股份有限公司 | The high-performance polyurethane elastomer and preparation method thereof of table tennis production |
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| CN111087965A (en) * | 2019-12-31 | 2020-05-01 | 深圳市真彩软胶科技有限公司 | Traceless removable adhesive for electronic equipment and preparation method thereof |
| CN111777983A (en) * | 2020-06-23 | 2020-10-16 | 山东一诺威聚氨酯股份有限公司 | High-hardness heat-conducting polyurethane structural adhesive and preparation method thereof |
| CN111675958A (en) * | 2020-07-08 | 2020-09-18 | 王振海 | Protective coating material for ships, naval vessels and offshore drilling platforms and preparation method |
| 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 |
| CN112876638A (en) * | 2021-01-08 | 2021-06-01 | 东莞市中森新材料有限公司 | Formula and production process of non-adhesive polyurethane elastomer |
| CN114149733A (en) * | 2021-12-07 | 2022-03-08 | 黎明化工研究设计院有限责任公司 | Transparent double-component aliphatic polyurethane coating with ultrahigh hardness and preparation method thereof |
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