CN104448791B - 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, and in particular to a kind of high-hard, transparent polyurethane elastomer and its preparation
Method.
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.With
The development of polyurethane cause, the purposes of polyurethane products also more and more extensively, to the performance requirement of product also more and more higher.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of high-hard, transparent polyurethane elastomer, have
Diversified aesthetic effect, and quality is very hard, and with yellowing resistance and toughness higher, the present invention also provides it
Preparation method, rational technology, it is easy to industrialized production.
High-hard, transparent polyurethane elastomer of the present invention, is made up of polymeric components and isocyano component：
Polymeric components are made up of the raw material of following percetage by weight：
Degree of functionality is the PPOX PPG 40%~91.85% that 3, number-average molecular weight is 400~5000,
Degree of functionality is 4, and number-average molecular weight is 300~600 PPOX PPG 5%~59.6%,
Antioxidant 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 percetage by weight：
Isocyanates 65%~73%, PPG 22%~35% and plasticizer 1%~5%.
Wherein：
Degree of functionality is that the PPOX PPG that 3, number-average molecular weight is 400~5000 is PPG400, PPG330N
Or one or more in PPG500；It is preferred that PPG500.
Degree of functionality is that the PPOX PPG that 4, number-average molecular weight is 300~600 is PPG430 or PPG600
In one or two；It is preferred that PPG430.
Antioxidant is antioxidant 1076 (β-positive octadecanol ester of (4- hydroxy phenyl -3,5- di-t-butyls) propionic acid) or antioxygen
One or two in agent 1010 (four (β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid) pentaerythritol esters).Antioxidant is
0.3~1%, preferably 0.5%.
Ultraviolet-resistant absorbent is UV328 (2- (the tertiary amyl phenyl of 2'- hydroxyls -3', 5'- bis-) BTA) or UV329
(2- (2'- hydroxyls -5'- spy octyl phenyl) BTA) in one or two.Ultraviolet-resistant absorbent is 0.2~0.6%,
It is preferred that 0.5%.
Catalyst is organic bismuth catalyst, organozinc catalyst or zinc bismuth composite metal catalyst one kind therein.Zinc bismuth
Composite metal catalyst is that organic bismuth catalyst and organozinc catalyst are mixed to get with arbitrary proportion.Organic bismuth catalyst is preferred
Bi content is 16% or 18% organic bismuth catalyst.Catalyst is common commercial products.
Isocyanates is one or two in liquefied mdi or MDI-50.
Diisocyanate is IPDI or H12One or two in MDI.
PPG is one or more in PPG500, PPG2000 or PPG3050, preferably PPG3050.
Plasticizer be DOTP, TXIB or DOP in one or two.Plasticizer is 1~10%, preferably 5%.
Appellation polymeric components of the present invention, prepolymer component are intended merely to the convenience in statement.
High-hard, transparent method for preparing polyurethane elastic body of the present invention, comprises the following steps：
(1) prepared by polymeric components
All raw materials of polymeric components are mixed, at 100~110 DEG C, is dehydrated to moisture under -0.095MPa and is less than
0.05%, obtain polymers compositions；
(2) prepared by prepolymer component
In terms of mass fraction, all raw materials of prepolymer component are mixed, reacted 2~3 hours at 70 DEG C~90 DEG C, obtained
Isocyano-content is 19%~19.5% prepolymer.
Wherein：
Polymeric components are individually packed with prepolymer component, during for production of articles, by polymeric components and prepolymer group
Part is 100 according to mass ratio：150 or 100:100 ratio mixing, mixing temperature is 25~35 DEG C, after stirring, pours into mould
In tool, cold curing, hardening time, the demoulding obtained transparent polyurethane elastomer at 8-10 minutes.Demoulding time is 15~20 points
Clock.
High-hard, transparent polyurethane elastomer of the present invention, is mainly used in replacing epoxy resin, make require environmental protection,
The high transparency material of good toughness, is used for making casting glue, nameplate, handicraft etc..
In sum, the present invention has advantages below：
(1) high-hard, transparent polyurethane elastomer transparency of the present invention is high, product stabilization, the polyurethane elastomer
Not only there is diversified aesthetic effect, and quality is very hard, is adapted to do some products instead of epoxy, can reach
The hardness and the transparency of epoxy resin, and with the incomparable yellowing resistance of epoxy and toughness.
(2) present invention provides its preparation method, rational technology, it is easy to industrialized production.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Following examples, are not specifically noted, and percentage refers both to mass percent.
All raw materials unless otherwise specified, are purchased in market in embodiment.
Embodiment material therefor:
PPG500 number-average molecular weights 500, polyoxypropylene trihydroxylic alcohol
PPG600 number-average molecular weights 600, polyoxypropylene tetrahydroxylic alcohol
PPG400 number-average molecular weights 400, polyoxypropylene trihydroxylic alcohol
PPG430 number-average molecular weights 300, polyoxypropylene tetrahydroxylic alcohol
PPG2000 number-average molecular weights 2000, polyoxypropylene dihydroxylic alcohols
PPG330N number-average molecular weights 5000, proportion of primary OH groups 75%, polyoxypropylene trihydroxylic alcohol
PPG3600 number-average molecular weights 5000, proportion of primary OH groups 75%, polyoxypropylene trihydroxylic alcohol
The polyoxypropylene trihydroxylic alcohol of PPG3050 number-average molecular weights 3000
The MDI of liquefied mdi Carbodiimide-Modified
MDI-50 4,4 '-methyl diphenylene diisocyanate 50% and 2,4 '-methyl diphenylene diisocyanate 50%
IPDI isoflurane chalcone diisocyanates
H12MDI hydrogenated diphenyl methane diisocyanates；
DOTP DOTPs
TXIB 2,2,4- trimethyl -1,3- pentanediol diisobutyrates.
Embodiment 1
Polymeric components：The PPG (PPG430) 5% of degree of functionality 4, molecular weight 300, degree of functionality 3, molecular weight 400
PPG (PPG400) 79%, degree of functionality 3, the PPG (PPG330N) 14.8% of molecular weight 5000, organo-bismuth
Catalyst 0.2%, antioxidant 1010 0.5%, ultra-violet absorber UV329 0.5%, at 100 DEG C, is dehydrated under -0.095MPa
0.05% is less than to moisture, polymers compositions is obtained.
Prepolymer component：It is with the degree of functionality of PPG (PPG2000) 24.5%, 3 of 2 degree of functionality molecular weight 2000 point
PPG (PPG3050) 10.5%, MDI-50 32.5% of son amount 3000, liquefied mdi 32.5% reacts 2.5 at 80 DEG C
Small vacuum (- 0.095MPa) removes bubble, obtains the prepolymer that isocyano-content is 19%.
By the temperature control of polymeric components and prepolymer component at 30 DEG C, according to 100：150 mass ratio mixing, stirs
Mix it is uniform after, in pouring into ready mould already, cold curing, hardening time, the demoulding in 18 minutes obtained Shao at 10 minutes
The high transparency polyurethane elastomer of family name 75D.
Embodiment 2：
Polymeric components：The PPG (PPG500) 91.85% of degree of functionality 3, molecular weight 500, degree of functionality 4, molecule
The PPG (430) 7% of amount 300, organozinc catalyst 0.15%, antioxidant 1076 0.5%, ultra-violet absorber
UV3280.5%, at 105 DEG C, is dehydrated to moisture less than 0.05% under -0.095MPa, obtains polymers compositions.
Prepolymer component：PPG (PPG3050) 32.3%, MDI-50 of 3 degree of functionality molecular weight 3000
34.7%, liquefied mdi 33% reacts 3 hours at 70 DEG C, vacuum (- 0.095MPa) removing bubble, obtains isocyano-content
It is 19% prepolymer.
By the temperature control of polymeric components and prepolymer component at 35 DEG C, according to 100：150 ratio mixing, stirring is equal
After even, in pouring into ready mould already, cold curing, hardening time, the demoulding in 20 minutes obtained shore 80D at 8 minutes
High transparency polyurethane elastomer material.
Embodiment 3：
Polymeric components：The PPG (PPG500) 90.85% of degree of functionality 3, molecular weight 500, degree of functionality 4, molecule
The PPG (430) 8% of amount 300, (organic bismuth catalyst and organozinc catalyst are with mass ratio 1 for zinc bismuth composite catalyst:
1 mixing) 0.15%, antioxidant 1076 0.5%, ultra-violet absorber UV328 0.5%, at 110 DEG C, is dehydrated under -0.095MPa
0.05% is less than to moisture, polymers compositions is obtained.
Prepolymer component：
Be with the PPG (PPG3050) 11% of 3 degrees of functionality, molecular weight 3000, degree of functionality 3, molecular weight 500 it is poly-
Ethoxylated polyhydric alcohol (PPG500) 11%, MDI-5032%, liquefied mdi 41%, TXIB 5% reacts 2 hours at 90 DEG C, vacuum (-
Bubble 0.095MPa) is removed, the prepolymer that isocyano-content is 19.5% is obtained.
By the temperature control of polymeric components and prepolymer component at 25 DEG C, according to 100：150 mass ratio mixing, stirs
Mix it is uniform after, in pouring into ready mould already, cold curing, hardening time at 10 minutes, 20 minutes can the demoulding, obtain
The high transparency polyurethane elastomer material of shore 85D.
Comparative example
Polymeric components：The PPG (PPG400) 40% of degree of functionality 3, molecular weight 400, degree of functionality 4, molecular weight
600 PPG (PPG600) 59.6%, mercury catalyst catalyst 0.4% is dehydrated under 100~110 DEG C, -0.095MPa
0.05% is less than to moisture, polymers compositions is obtained.
Isocyano component：The DOTP of IPDI 85% and 15% is mixed to get isocyanide of the isocyano-content 31%
Acid group component.
By the temperature control of polymeric components and prepolymer component at 30 DEG C, according to 100：100 mass ratio mixing, stirs
Mix it is uniform after, in pouring into ready mould already, cold curing, hardening time, the demoulding in 20 minutes obtained Shao at 5 minutes
The high transparency polyurethane elastomer material of family name 83D.
The product that embodiment 1-3 and comparative example are prepared carries out performance test, and test result is shown in Table 1.
The performance test results of the product that the embodiment 1-3 of table 1 and comparative example are prepared
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Hardness (Shao D) | 75D | 80D | 85D | 83D |
| The transparency | It is transparent | It is transparent | It is transparent | It is transparent |
| Toughness | It is excellent | It is excellent | It is excellent | Well |
Claims (10)
1. a kind of high-hard, transparent polyurethane elastomer, it is characterised in that：It is made up of polymeric components and isocyano component：
Polymeric components are made up of the raw material of following percetage by weight：
Degree of functionality is the PPOX PPG 40%~91.85% that 3, number-average molecular weight is 400~5000,
Degree of functionality is 4, and number-average molecular weight is 300~600 PPOX PPG 5%~59.6%,
Antioxidant 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 percetage by weight：
Isocyanates 65%~73%, PPG 22%~35% and plasticizer 1%~5%；The isocyano of prepolymer component
Content is 19%~19.5%.
2. high-hard, transparent polyurethane elastomer according to claim 1, it is characterised in that：
Degree of functionality be PPOX PPG that 3, number-average molecular weight is 400~5000 for PPG400, PPG330N or
One or more in PPG500；
Degree of functionality is PPOX PPG that 4, number-average molecular weight is 300~600 in PPG430 or PPG600
One or two.
3. high-hard, transparent polyurethane elastomer according to claim 1, it is characterised in that：Antioxidant is antioxidant 1076
Or one or two in antioxidant 1010；Ultra-violet absorber be UV328 or UV329 in one or two.
4. high-hard, transparent polyurethane elastomer according to claim 1, it is characterised in that：It is organic bismuth catalyst, organic
Zinc catalyst or zinc bismuth composite metal catalyst one kind therein.
5. high-hard, transparent polyurethane elastomer according to claim 1, it is characterised in that：Isocyanates is liquefied mdi
Or one or two in MDI-50.
6. high-hard, transparent polyurethane elastomer according to claim 1, it is characterised in that：Diisocyanate be IPDI or
H12One or two in MDI.
7. high-hard, transparent polyurethane elastomer according to claim 1, it is characterised in that：PPG is
One or more in PPG500, PPG2000 or PPG3050.
8. high-hard, transparent polyurethane elastomer according to claim 1, it is characterised in that：Plasticizer is DOTP, TXIB
Or one or two in DOP.
9. any described high-hard, transparent method for preparing polyurethane elastic body of a kind of claim 1-8, it is characterised in that：Bag
Include following steps：
（1）It is prepared by polymeric components
All raw materials of polymeric components are mixed, dehydration to moisture is less than 0.05%, obtains polymers compositions；
（2）It is prepared by prepolymer component
In terms of mass fraction, all raw materials of prepolymer component are mixed, reacted 2~3 hours at 70 DEG C~90 DEG C, obtain isocyanide
Acid group content is 19%~19.5% prepolymer.
10. high-hard, transparent method for preparing polyurethane elastic body according to claim 9, it is characterised in that：Polymer
Component is individually packed with prepolymer component, during for production of articles, is according to mass ratio with prepolymer component by polymeric components
100：150 or 100:100 ratio mixing, mixing temperature is 25 ~ 35 DEG C, after stirring, in pouring into mould, cold curing,
Hardening time, the demoulding obtained transparent polyurethane elastomer at 8-10 minutes.
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