CN109232856B - Preparation method of high-permeability high-elasticity polyurethane elastomer - Google Patents
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
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Abstract
The invention relates to a preparation method of a high-permeability high-elasticity polyurethane elastomer, belonging to the technical field of polyurethane application. PTMG, HDO, catalyst and antioxidant are mixed evenly according to a certain mass ratio under the condition of room temperature, and then are sealed and stored; the PTMG and isocyanate react for 2-3 hours at 80-85 ℃, the vacuum degree is not less than-0.095 MPa, and a polyurethane prepolymer component with the isocyanate content of 8.5-13.2% is obtained; and (2) controlling the polymer component and the polyurethane prepolymer component to be mixed at 60-80 ℃, uniformly mixing the polymer component and the polyurethane prepolymer component according to the ratio of 40-100: 100, pouring the mixture into a mold at 70-90 ℃, and opening the mold for 30-45 minutes to obtain the high-permeability high-elasticity polyurethane elastomer. The high-permeability high-elasticity polyurethane elastomer prepared by the method has the characteristics of higher transparency, rebound resilience and yellowing resistance, and meets the market demand on the high-permeability high-elasticity polyurethane elastomer.
Description
Technical Field
The invention relates to a preparation method of a high-permeability high-elasticity polyurethane elastomer, belonging to the technical field of polyurethane application.
Background
Polyurethane is a high molecular synthetic material with the performance between that of rubber and plastic, and is characterized by wide hardness adjustment range, elasticity of rubber and hardness of plastic, and good mechanical property, wear resistance and resilience, and becomes the most rapidly developed high molecular material after PE, PP, PVC, PS and phenolic resin. The transparent polyurethane elastomer not only has excellent optical performance, but also has the hardness range with very wide polyurethane elasticity and higher mechanical strength, is suitable for optics, ballistic launch, artware manufacture and the like, and can be used for manufacturing spectacle lenses, bulletproof glass, trademark nameplates and the like. The type of isocyanate, the type of chain extender, the type and molecular weight of the polyol, etc., all affect the mechanical properties and optical stability of the polyurethane elastomer.
Elastomers synthesized with polyester polyols contain highly polar ester groups, which tend to crystallize and affect the transparency of polyurethane elastomers. And the polyether polyol has weak intermolecular interaction, the product has low crystallinity, and the polyurethane elastomer with high transparency can be prepared more easily. Propylene oxide polyether (PPG) is the most common polyether polyol and has the advantages of low price, small viscosity at room temperature and convenient use, but the elastomer prepared by using the PPG has poor resilience and needs to be improved in mechanical property.
CN101134843A discloses a preparation method of a high-elasticity polyurethane elastomer, PTMG2000 or PPG3000 is mixed with BDO, a catalyst and an anti-aging agent to be used as a polymer component, isocyanate in a prepolymer component is selected from MDI, carbodiimide modified MDI and a mixture thereof, and the prepared high-elasticity elastomer has narrow hardness range (Shore A80 +/-2) and poor resilience.
The isocyanate commonly used for synthesizing the polyurethane elastomer is mainly aromatic diisocyanate TDI and MDI, and the polyurethane elastomer synthesized by adopting the two isocyanates contains a bridge bond of aromatic urea due to the existence of a benzene ring, and a colored quinoid structure is easily generated once the polyurethane elastomer is irradiated by ultraviolet light, so that a product is yellowed, and the transparency is reduced. In order to solve the problems, a method for preparing a high-permeability high-elasticity polyurethane elastomer is explored.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a high-permeability high-elasticity polyurethane elastomer. The high-permeability high-elasticity polyurethane elastomer prepared by the method has a wider hardness range, higher transparency and rebound resilience, and yellowing resistance, and meets the market demand on the high-permeability high-elasticity polyurethane elastomer.
The preparation method of the high-permeability high-elasticity polyurethane elastomer comprises the following steps:
(1) preparation of the Polymer component
PTMG, HDO, catalyst and antioxidant are mixed evenly according to a certain mass ratio under the condition of room temperature, and then are sealed and stored;
(2) preparation of the polyurethane prepolymer component
The PTMG and isocyanate react for 2-3 hours at 80-85 ℃, the vacuum degree for removing bubbles is not less than-0.095 MPa, and a polyurethane prepolymer component with the content of isocyanate groups being 8.5-13.2% is prepared;
(3) preparation of polyurethane elastomers
Controlling the mixing temperature of the polymer component and the polyurethane prepolymer component at 60-80 ℃, uniformly mixing the polymer component and the polyurethane prepolymer component according to the ratio of 40-100: 100, pouring into a mold at 70-90 ℃, opening the mold for 30-45 minutes without vulcanization, and obtaining the high-permeability high-elasticity polyurethane elastomer.
Wherein:
the molecular weight of PTMG in the step (1) and the step (2) is 1000-2000, the water content of PTMG is less than or equal to 0.03 percent, and PTMG is one or two of PTMG1000 or PTMG 2000; the catalyst is an organic bismuth catalyst.
The polymer component in the step (1) consists of PTMG, HDO, a catalyst and an antioxidant, and the mass fraction of the polymer component is 10000-62.5% of PTMG, 20000-93% of PTMG, 6-38.3% of HDO, 0.4-0.7% of the catalyst and 0.5% of the antioxidant; the above mass fractions are all mass portions of the polymer component.
The polyurethane prepolymer component comprises PTMG and isocyanate; the PTMG is one or two of PTMG1000 or PTMG 2000.
PTMG1000 accounts for 0-10.7 wt% of the polyurethane prepolymer component, and PTMG2000 accounts for 43-66.4 wt% of the polyurethane prepolymer component.
The isocyanate is aromatic isocyanate or mixture of aromatic isocyanate and aliphatic isocyanate, the aromatic isocyanate is MDI-100, and the aliphatic isocyanate is H12One or two of MDI and IPDI, and the aliphatic isocyanate accounts for 0-20% of the total amount of the isocyanate.
By mass fraction, aliphatic isocyanate H12MDI accounts for 0-4.3% of the polyurethane prepolymer component, and IPDI accounts for 0-9.3% of the polyurethane prepolymer component; the aromatic isocyanate MDI-100 accounts for 33.6 to 38.7 percent of the polyurethane prepolymer component.
The hardness of the polyurethane elastomer is Shore A65-95; resilience is 75-85%; the light transmittance is not less than 89%, and the highest light transmittance is 96%; the haze is less than or equal to 1.1 percent, and the minimum value reaches 0.6 percent.
As a preferred technical scheme, the preparation method of the high-permeability high-elasticity polyurethane elastomer specifically comprises the following steps:
the invention adopts a bi-component system, the bi-component combined material comprises a polymer component and a prepolymer component which are respectively named as a component A and a component B, and the related content percentages are weight percentages.
(1) The preparation method of the component A comprises the following steps: a mixture is prepared by mixing PTMG, HDO, a catalyst and an antioxidant in percentage by weight, and PTMG 10000-62.5% or PTMG 20000-93% and HDO 6-38.3% and catalyst 0.4-0.7% and antioxidant 0.5% are uniformly mixed at room temperature and then are sealed and stored.
The type and the portion of the polyether polyol can be reasonably adjusted within the range according to the performance of the required product; the content of the catalyst can be selected within the above range according to the requirements of the actual reaction.
(2) The preparation method of the component B comprises the following steps: a prepolymer, wherein PTMG and isocyanate react for 2-3 hours at 80-85 ℃, the water content of PTMG is preferably less than or equal to 0.03%, PTMG 10000-10.7%, PTMG 200043-66.4%, isocyanate can be selected from MDI-10033.6-38.7%, H120-4.3% of MDI, 0-9.3% of IPDI, and preferably, the degree of vacuum for removing bubbles is not less than-0.095 MPa, and the content of isocyanate in the obtained prepolymer is 8.5-13.2%.
(3) Preparation of polyurethane elastomers
Controlling the mixing temperature of the polymer component and the polyurethane prepolymer component at 60-80 ℃, uniformly mixing the polymer component and the polyurethane prepolymer component according to the ratio of 40-100: 100, pouring into a mold at 70-90 ℃, opening the mold for 30-45 minutes without vulcanization, and obtaining the high-permeability high-elasticity polyurethane elastomer.
The invention improves the transparency of the polyurethane elastomer, firstly, the chain length of the chain extender is increased, HDO with longer molecular chain is adopted as the chain extender,and reducing the molecular weight (number average molecular weight 1000) of polyether polyol to shorten the length of a soft segment chain and prevent the formation of perfect crystals, and introducing aliphatic diisocyanate H not containing benzene rings12MDI and IPDI are used as isocyanate to avoid yellowing of the product. In view of improving the transparency of the product without losing the mechanical property and enabling the product to have high elasticity, the invention adopts polytetramethylene ether glycol (PTMG) as a polyol, and adds PTMG2000 with a certain proportion in the formula of the product with low hardness to improve the rebound of the product. Thereby providing a preparation method of the high-permeability high-elasticity polyurethane elastomer, and being used for preparing large products with high hardness.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-permeability high-elasticity polyurethane elastomer prepared by the method has high transparency and rebound resilience, has the yellowing resistance, and can meet the market demand on the high-permeability high-elasticity polyurethane elastomer.
(2) The method for preparing the high-permeability high-elasticity polyurethane elastomer has the advantages of simple operation, excellent processing property, energy conservation, low requirement on equipment and the like.
(3) The hardness Shore A of the polyurethane elastomer prepared by the method is 65-95; resilience is 75-85%; the light transmittance is not less than 89%, and the highest light transmittance is 96%; the haze is less than or equal to 1.1 percent, and the minimum value reaches 0.6 percent.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The two-component high-permeability high-elasticity polyurethane elastomer comprises the following components:
the component A comprises: 93 percent and 7 percent of PTMG2000 and HDO with the water content less than or equal to 0.03 percent respectively, 0.4 percent of bismuth catalyst, and antioxidants UV-10760.2 percent and UV-3280.3 percent which are uniformly mixed to obtain the component A.
And B component: and (3) reacting PTMG 200066.4% with the water content of less than or equal to 0.03% and MDI-10033.6% at 85 ℃ for 2.5 hours, and removing bubbles in vacuum (-0.095MPa) to obtain a prepolymer with the isocyanate content of 8.5%.
A. The mixing temperature of the two components B is controlled at 65 ℃, and the weight ratio of the two components A: b is 100:100, pouring the mixture into a mold at 75 ℃, opening the mold for 40 minutes, and obtaining the high-permeability high-elasticity polyurethane elastomer with the hardness of Shore 65A and the rebound of 85 percent.
Example 2
The two-component high-permeability high-elasticity polyurethane elastomer comprises the following components:
the component A comprises: PTMG1000 with the water content less than or equal to 0.03 percent, PTMG2000 and HDO respectively 25 percent, 65 percent and 10 percent, bismuth catalyst 0.5 percent, antioxidant UV-10760.2 percent and UV-3280.3 percent, and evenly mixing to obtain the component A.
And B component: PTMG 200063% with water content less than or equal to 0.03% and MDI-10037% react at 85 deg.c for 2.5 hr, and vacuum (-0.095MPa) is used to eliminate bubble to obtain prepolymer with isocyanate radical content of 9.8%.
A. The mixing temperature of the two components B is controlled at 65 ℃, and the weight ratio of the two components A: b-80: 100, pouring the mixture into a mold at 75 ℃, opening the mold for 40 minutes, and obtaining the high-permeability high-elasticity polyurethane elastomer with the hardness of Shore 75A and the resilience of 82%.
Example 3
The two-component high-permeability high-elasticity polyurethane elastomer comprises the following components:
the component A comprises: PTMG1000 with the water content less than or equal to 0.03 percent, PTMG2000 and HDO respectively 41.7 percent, 38.3 percent and 20 percent, bismuth catalyst 0.6 percent, antioxidant UV-10760.2 percent and UV-3280.3 percent, and the component A is obtained by uniformly mixing.
And B component: PTMG 200057% and MDI-10038.7% with water content ≦ 0.03%, H124.3 percent of MDI reacts for 2 hours at 85 ℃, and bubbles are removed in vacuum (-0.095MPa), thus obtaining the prepolymer with 12 percent of isocyanate.
A. The mixing temperature of the two components B is controlled at 65 ℃, and the weight ratio of the two components A: b is 60: 100, pouring the mixture into a mold at 75 ℃, opening the mold for 40 minutes, and obtaining the high-permeability high-elasticity polyurethane elastomer with the hardness of Shore 85A and the rebound of 79 percent.
Example 4
The two-component high-permeability high-elasticity polyurethane elastomer comprises the following components:
the component A comprises: 62.5 percent and 37.5 percent of PTMG1000 and HDO with the water content less than or equal to 0.03 percent respectively, 0.7 percent of bismuth catalyst, and antioxidants UV-10760.2 percent and UV-3280.3 percent which are evenly mixed to obtain the component A.
And B component: PTMG 100010.7% with the moisture content less than or equal to 0.03%, PTMG 200043% and MDI-10037%, IPDI 9.3% reacts for 2 hours at 85 ℃, and bubbles are removed in vacuum (-0.095MPa), thus obtaining the prepolymer with the isocyanate content of 13.2%.
A. The mixing temperature of the two components B is controlled at 65 ℃, and the weight ratio of the two components A: b is 40: 100, pouring the mixture into a mold at 75 ℃, opening the mold for 40 minutes, and obtaining the high-permeability high-elasticity polyurethane elastomer with the hardness of Shore 90A and the resilience of 75 percent.
Comparative example 1
The component A comprises: 86.4 percent and 13.6 percent of PTMG2000 and BDO respectively with the moisture content less than or equal to 0.03 percent, 0.6 percent of bismuth catalyst, 0.2 percent and 0.3 percent of antioxidant UV-1076 and UV-328 respectively, and evenly mixing to obtain the component A.
And B component: PTMG 200057% and MDI-10038.7% with water content ≦ 0.03%, H124.3 percent of MDI reacts for 2 hours at 85 ℃, and bubbles are removed in vacuum (-0.095MPa), thus obtaining the prepolymer with 12 percent of isocyanate.
A. The mixing temperature of the two components B is controlled at 65 ℃, and the weight ratio of the two components A: b is 60: 100, pouring the mixture into a mold at 75 ℃, opening the mold for 40 minutes, and obtaining the high-permeability high-elasticity polyurethane elastomer with the hardness of Shore 85A and the resilience of 70 percent.
The polyurethane elastomers prepared in examples 1 to 4 and comparative example 1 were subjected to property detection, and the light transmittance and haze of the product were measured by using a haze transmittance meter model SGW-810, manufactured by guangzhou packaging equipment ltd, under the following conditions: after the machine is started and preheated for 20min, at room temperature, a sample slice with the thickness of 2mm is placed in a colorimetric device and fixed by a positioning clamp, so that the sample slice is close to the wall of the colorimetric device seat, after the instrument is continuously calibrated for multiple times, the sample to be tested is pushed into a light path, and the visible light transmittance of the sample can be tested. The results of the performance tests of examples 1-4 and comparative example 1 are shown in Table 1.
TABLE 1 results of Performance test of examples 1-4 and comparative example 1
Table 1 shows the performance test results of the polyurethane elastomers obtained in examples 1 to 4 of the present invention and comparative example 1, and it can be seen from comparison with comparative example 1 that the polyurethane elastomer prepared by using the polymer component containing 1, 6-hexanediol of the present invention has significantly improved transparency, significantly increased light transmittance, and reduced haze. Comparing example 3 with comparative example 1, the article of example 3 has a higher rebound when the elastomer hardness is the same. And in examples 1-4, the light transmittance of the elastomer increased with the increase in the proportion of HDO. Along with the reduction of the proportion of PTMG1000 and the increase of the proportion of PTMG2000 in the polymer components, the rebound rate of the high-permeability polyurethane elastomer is obviously improved, which is mainly because the soft segment proportion is increased and the flexibility of the molecular chain is increased due to the increase of the molecular weight of the polyol.
Claims (3)
1. A preparation method of a high-permeability high-elasticity polyurethane elastomer is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) preparation of the Polymer component
PTMG, HDO, catalyst and antioxidant are mixed evenly according to a certain mass ratio under the condition of room temperature, and then are sealed and stored;
(2) preparation of the polyurethane prepolymer component
The PTMG and isocyanate react for 2-3 hours at 80-85 ℃, the vacuum degree for removing bubbles is more than or equal to-0.095 MPa, and a polyurethane prepolymer component with the content of isocyanic acid radical of 8.5-13.2% is prepared;
(3) preparation of polyurethane elastomers
Controlling the mixing temperature of the polymer component and the polyurethane prepolymer component at 60-80 ℃, uniformly mixing the polymer component and the polyurethane prepolymer component according to the ratio of 40-100: 100, pouring into a mold at 70-90 ℃, opening the mold for 30-45 minutes without vulcanization, and obtaining the high-permeability high-elasticity polyurethane elastomer;
the water content of PTMG in the step (1) and the step (2) is less than or equal to 0.03 percent; the polymer component in the step (1) consists of PTMG, HDO, a catalyst and an antioxidant, wherein the PTMG is one or two of PTMG1000 or PTMG2000, and in mass fraction, the PTMG1000 accounts for 0-62.5% of the polymer component, the PTMG2000 accounts for 0-93% of the polymer component, the HDO accounts for 6-38.3% of the polymer component, the catalyst accounts for 0.4-0.7% of the polymer component, and the antioxidant accounts for 0.5% of the polymer component;
the polyurethane prepolymer component in the step (2) consists of PTMG and isocyanate; PTMG is PTMG2000 or a mixture of PTMG2000 and PTMG 1000; the PTMG1000 accounts for 0-10.7 wt% of the polyurethane prepolymer component, and the PTMG2000 accounts for 43-66.4 wt% of the polyurethane prepolymer component; the isocyanate is aromatic isocyanate or mixture of aromatic isocyanate and aliphatic isocyanate, the aromatic isocyanate is MDI-100, and the aliphatic isocyanate is H12One or two of MDI and IPDI, and the aliphatic isocyanate accounts for 0-20% of the total amount of the isocyanate; by mass fraction, aliphatic isocyanate H12MDI accounts for 0-4.3% of the polyurethane prepolymer component, and IPDI accounts for 0-9.3% of the polyurethane prepolymer component; the aromatic isocyanate MDI-100 accounts for 33.6 to 38.7 percent of the polyurethane prepolymer component.
2. The preparation method of the high-permeability high-elasticity polyurethane elastomer according to claim 1 is characterized in that: the catalyst is an organic bismuth catalyst; the antioxidant is a mixture of UV-328 and UV-1076.
3. The preparation method of the high-permeability high-elasticity polyurethane elastomer according to claim 1 is characterized in that: the hardness Shore A of the polyurethane elastomer is 65-95; resilience is 75-85%; the light transmittance is more than or equal to 89 percent and can reach 96 percent maximally; the haze is less than or equal to 1.1 percent and the lowest haze is 0.6 percent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810879295.2A CN109232856B (en) | 2018-08-03 | 2018-08-03 | Preparation method of high-permeability high-elasticity polyurethane elastomer |
| PCT/CN2018/122976 WO2020024538A1 (en) | 2018-08-03 | 2018-12-24 | Method for preparing polyurethane elastomer with high transparency and high elasticity |
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| CN201810879295.2A CN109232856B (en) | 2018-08-03 | 2018-08-03 | Preparation method of high-permeability high-elasticity polyurethane elastomer |
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| CN109232856B true CN109232856B (en) | 2021-04-09 |
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| CN112538149B (en) * | 2019-09-23 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation process of casting polyurethane elastomer |
| CN112574386B (en) * | 2020-12-03 | 2022-08-05 | 万华化学集团电子材料有限公司 | Method for producing cast polyurethane elastomers with improved light transmission and use thereof as polishing pad window material |
| CN113416153A (en) * | 2021-05-28 | 2021-09-21 | 岳阳昌德新材料有限公司 | Alicyclic diisocyanate and preparation method and application thereof |
| CN113831502B (en) * | 2021-10-22 | 2023-06-23 | 东莞市米儿塑胶原料有限公司 | Preparation method of high-hardness transparent TPU |
| CN114853977B (en) * | 2022-04-27 | 2023-03-24 | 盛鼎高新材料有限公司 | High-permeability high-elasticity polyurethane elastomer and preparation method thereof |
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