CN110172134B - Hydrolysis-resistant polyurethane pultrusion resin composite material and preparation method thereof - Google Patents
Hydrolysis-resistant polyurethane pultrusion resin composite material and preparation method thereof Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
The invention discloses a hydrolysis-resistant polyurethane pultrusion resin composite material and a preparation method thereof, and belongs to the field of two-component polyurethane resin. The preparation method comprises the steps of S1, preparing hydrolysis-resistant polyurethane prepolymer from the component B; step S2, preparing a component A polyol crosslinking agent; step S3, transferring the two components in the step S1 and the step S2 to two storage tanks of a two-component glue supply system respectively; and step S4, curing and molding the continuous fibers soaked with the resin through a high-temperature mold by a two-component polyurethane pultrusion system. The polyurethane-based glass fiber reinforced plastic composite material prepared by the steps has the characteristics of high mechanical strength, good hydrolysis resistance and the like.
Description
Technical Field
The invention belongs to the field of double-component polyurethane resin, and particularly relates to a hydrolysis-resistant polyurethane pultrusion resin composite material and a preparation method thereof.
Background
The pultrusion process is simple and general, when the fiber soaked with resin passes through a high-temperature die, the resin is cured under the tension of a tractor and is pultruded and formed, and the pultrusion process has the advantages of simple and efficient process, continuous production, high fiber content of products and the like. The traditional pultrusion process mostly adopts unsaturated resin, vinyl resin, epoxy resin and the like, the unsaturated resin and the vinyl resin contain a large amount of styrene and are harmful to people and environment, and curing agents are mostly peroxides, so that the epoxy resin is flammable, explosive and not easy to store; epoxy resin is slow to cure, the production efficiency is extremely low, and under most conditions, the product is hard and brittle and has insufficient toughness.
The polyurethane resin has the advantages of high curing speed, high production efficiency, strong product performance, more friendliness to people and environment and the like, and the application of the polyurethane resin in a pultrusion process is gradually increased in recent years. Polyurethane resin for the existing pultrusion process is prepared by taking polyphenyl methane polyisocyanate (polymeric MDI) as a component B and taking polyether polyol mixture as a component A, and is used for preparing composite materials. For example, the first prior art discloses a preparation method of a two-component polyurethane resin for pultrusion process, which takes polymeric MDI as a component B and a polyether polyol mixture as a component A; the second prior art discloses a preparation method of a double-component polyurethane resin with a flame retardant function, wherein a base resin is prepared by taking polymeric MDI as a component B and a polyether polyol mixture as a component A and adding a flame retardant on the basis of the base resin.
Polyether type resins have good water resistance but inferior mechanical properties to polyester type resins, and some inventions modify polyurethane resin formulations for this reason. As patent prior art three and prior art four disclose preparation methods for preparing polyester type polyurethane resin, but no clear description is made on how to improve hydrolysis resistance of polyester; the fifth patent prior art discloses a method for preparing two-component polyester type polyurethane resin, wherein the component B is still polymeric MDI, and in order to solve the problem that polyester is easy to hydrolyze, a method of adding expensive hydrolysis resistance agent is adopted; in the sixth prior art, a method for preparing polyester-polyether hybrid resin is disclosed, wherein the mechanical property of the resin can be improved by adding a certain proportion of polycarbonate diol into a polyether polyol mixture, but the problem of polycarbonate hydrolysis is not considered, and meanwhile, the addition of polycarbonate can improve the overall viscosity of the resin and is not beneficial to the infiltration of the resin and fibers.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects of the prior art, the invention provides a method for preparing a component B with both hydrophobicity and hydrolysis resistance, a two-component polyurethane resin which is composed of the component B and a polyester component A and has excellent mechanical property and hydrolysis resistance, and a composite material which is prepared by a pultrusion process by using the resin as a base material and a continuous fiber reinforced material.
The technical scheme is as follows: a preparation method of a hydrolysis-resistant polyurethane pultrusion resin composite material comprises the following steps:
step S1, preparing a hydrolysis-resistant polyurethane prepolymer as the component B, vacuumizing polyol with a hydrophobic function at 120 ℃ for 2h, cooling to 80 ℃, adding excessive carbodiimide modified isocyanate, and reacting at the temperature for 2-3 h to obtain the polyurethane prepolymer with a certain NCO content;
step S2, preparing the A-component polyol crosslinking agent, wherein the A-component polyol crosslinking agent comprises the following components in parts by weight:
55-80 wt% of polyester polyol;
10-20 wt% of vegetable oil polyol;
2-8 wt% of a release agent;
2-5 wt% of a water removing agent;
0.2-1 wt% of a catalyst;
0-25 wt% of filler;
0.5-1 wt% of ultraviolet absorbent;
0.5-1 wt% of an anti-aging agent;
step S3, transferring the two components in the step S1 and the step S2 to 2 storage tanks of a bi-component glue supply system respectively;
and step S4, curing and molding the continuous fibers soaked with the resin through a high-temperature mold by a two-component polyurethane pultrusion system.
In a further embodiment, the polyol having the hydrophobic function in the step S1 is one of castor oil polyol or hydroxyl-terminated polybutadiene polyol having a molecular weight of 1000g/mol and 2000 g/mol; the anti-aging agent is one of 2, 5-di-tert-butyl hydroquinone or dioctadecyl thiodipropionate;
in a further embodiment, the NCO content of the prepolymer finally obtained in step S1 is 15% to 27%.
In a further embodiment, the vegetable oil polyol in step S2 is a castor oil polyol; the water removing agent is a 3A activated molecular sieve, and is baked for more than 6 hours at 250 ℃ before use; the catalyst is a delayed type catalyst; the filler is one of calcium carbonate, aluminum hydroxide and talcum powder; the ultraviolet absorbent is one of benzophenone or benzotriazole.
In a further embodiment, the two-component glue supply system in step S3 includes two metering pumps respectively connected below the a material tank, the B material tank, and the AB material tank, and modules such as a static mixer for mixing the AB material, the glue injection frequency is 0.2 to 2Hz, and the glue injection amount is 50 to 200 g/time.
In a further embodiment, the two-component polyurethane pultrusion system in the step S4 includes modules such as a creel, a yarn guide device, a glue injection box, a segmented heating mold and a tractor; the glue supply system is connected with the glue injection box in a sealing mode, the segmented heating mold is heated in three zones, the temperature ranges of the two zones are 150-250 ℃, the temperature range of the third zone is room temperature-180 ℃, and the traction speed of the tractor is 10-280 cm/min.
In a further embodiment, the step S4 includes the following four steps:
s401, mixing the material A and the material B which are beaten out by a metering pump according to a certain proportion by a static mixer, and then feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
s402, enabling continuous fibers led out of a creel to enter a glue injection box at a certain tension and a certain speed under the driving of a traction machine through a yarn guide device, and fully mixing and infiltrating the continuous fibers with resin which is beaten into the glue injection box in the step S401;
and S403, heating the front section and the middle section of the mold, wherein the continuous fibers soaked by the resin are positioned at about 2/3 of the total length of the mold, and the resin is quickly cured under the combined action of temperature and a catalyst to form the composite material with strength.
And S404, slightly shrinking while curing the resin, and demolding at the tail section of the mold under the combined action of the mold release agent.
Has the advantages that: the invention relates to a hydrolysis-resistant polyurethane pultrusion resin composite material and a preparation method thereof, resin with mechanical property and hydrolysis resistance can be obtained by the method provided by the invention, and the hydrolysis resistance principle is that a large number of carbodiimide groups on oligomer in a component B can rapidly generate crosslinking reaction with carboxyl generated by polyester hydrolysis, so that the broken polyester molecular chain is rapidly re-linked to a crosslinking network in the polymer by carbodiimide, and the integral mechanical property of the resin is ensured not to be reduced.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents and instruments of any manufacturer are commercially available.
Example 1
A preparation method of a hydrolysis-resistant polyurethane pultrusion resin composite material comprises the following steps:
preparation of the component B: 93 kg of castor oil is weighed and added into a closed reaction kettle, the temperature is raised to 120 ℃, the stirring and the vacuumizing are carried out, the vacuumizing and the heating are stopped after 2h, the temperature is reduced to 80 ℃, 121.6 kg of carbodiimide modified MDI (Vanhua company) with the trade name of 100LL is added, and the reaction is continued for 2h to obtain the prepolymer with the NCO content of 27 percent.
Preparation of component A: 80 kg of polyester 2915 (Spodopan company), 10 kg of castor oil polyol, 8 kg of 550D mold release agent (Technick Products company), 2 kg of 3A activated molecular sieve which has been baked at high temperature, 1 kg of FOMREZ UL-28 and 0.5 kg of K-5218 which are used as catalysts, 1 kg of benzophenone serving as an ultraviolet absorbent and 1 kg of 2, 5-ditert-butylhydroquinone serving as an anti-aging agent are respectively weighed and added into a stirring kettle and stirred uniformly.
Respectively introducing the component A and the component B into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, enabling glass fibers to form a certain tension from a creel through a yarn guide plate under the drive of a tractor, enabling the glass fibers to pass through a glue injection box connected with the bi-component glue supply system (the glue injection frequency of the bi-component glue supply system is 2Hz, the glue injection amount is 200g each time, the weight ratio of the material B to the material A is 1: 1) at a speed of 280cm/min, enabling the bi-component glue supply system and the material B to be fully soaked with mixed resin of the component AB, enabling the mixed resin to enter a mold (the three temperatures are respectively 150 ℃, 180 ℃ and 160 ℃), and enabling the resin to be cured and molded at a high temperature and to leave the mold.
And (3) testing mechanical properties: testing the tensile strength, the tensile modulus, the elongation at break, the bending strength and the bending modulus of the prepared composite material according to the national standard GB/T16421-1996;
and (3) hydrolysis resistance test: the sample bars prepared according to the above standard are placed in a humid heat aging box with 85 ℃ and 85% humidity for 1000h, and then taken out to test the mechanical property and the reduction ratio of the sample bars.
Example 2
Preparation of the component B: weighing 100 kg of hydroxyl-terminated polybutadiene with the molecular weight of 1000g/mol, adding the hydroxyl-terminated polybutadiene into a closed reaction kettle, heating to 120 ℃, stirring and vacuumizing, stopping vacuumizing and heating after 2h, cooling to 80 ℃, adding 54.5 kg of carbodiimide modified MDI (Hensman company) with the trade name of 2020, and continuing to react for 2h to obtain a prepolymer with the NCO content of 15%.
Preparation of component A: 55 kg of polyester 3050 (Pasteur), 20 kg of castor oil polyol, 2 kg of 1948MCH mold release agent (AXEL Plastics), 5 kg of 3A activated molecular sieve which has been baked at high temperature, 0.1 kg of FOMREZ UL-29 and 0.1 kg of K-5218 which are 1 kg in total, 25 kg of aluminum hydroxide filler, 0.5 kg of ultraviolet absorber benzotriazole and 0.5 kg of anti-aging agent dioctadecyl thiodipropionate are respectively weighed and added into a stirring kettle and stirred uniformly.
Respectively introducing the component A and the component B into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, enabling glass fibers to form a certain tension from a creel through a yarn guide plate under the drive of a tractor, enabling the glass fibers to pass through a glue injection box connected with the bi-component glue supply system (the glue injection frequency of the bi-component glue supply system is 0.2Hz, the glue injection amount is 50g each time, and the weight ratio of the material B to the material A is 1.6: 1) at a speed of 10cm/min, enabling the glass fibers to be fully soaked with mixed resin of the component AB, enabling the mixed resin to enter a mold (the three temperatures are respectively 200 ℃, 250 ℃ and room temperature), and enabling the resin to be cured and formed at a high temperature and to leave the.
And (3) testing mechanical properties: the prepared composite material is tested for tensile strength, tensile modulus, elongation at break, flexural strength and flexural modulus according to the national standard GB/T16421-1996.
And (3) hydrolysis resistance test: the sample bars prepared according to the above standard are placed in a humid heat aging box with 85 ℃ and 85% humidity for 1000h, and then taken out to test the mechanical property and the reduction ratio of the sample bars.
Example 3
Preparation of the component B: weighing 100 kg of hydroxyl-terminated polybutadiene with molecular weight of 2000g/mol, adding the hydroxyl-terminated polybutadiene into a closed reaction kettle, heating to 120 ℃, stirring and vacuumizing, stopping vacuumizing and heating after 2h, cooling to 80 ℃, adding 63.6 kg of carbodiimide modified MDI (Pasteur company) with the brand number of MM103C, and continuing to react for 2h to obtain the prepolymer with the NCO content of 20%.
Preparation of component A: 70 kg of polyester 3050 (Pasteur), 15 kg of castor oil polyol, 4 kg of 1948MCH mold release agent (AXEL Plastics), 3 kg of 3A activated molecular sieve which has been baked at high temperature, 0.4 kg of FOMREZ UL-29 as a catalyst and 0.3 kg of K-5218 of 0.7 kg in total, 10 kg of calcium carbonate filler, 0.75 kg of ultraviolet absorber benzotriazole and 0.75 kg of anti-aging agent dioctadecyl thiodipropionate are respectively weighed and added into a stirring kettle and stirred uniformly.
Respectively introducing the component A and the component B into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, enabling glass fibers to form a certain tension from a creel through a yarn guide plate under the drive of a tractor, enabling the glass fibers to pass through a glue injection box connected with the bi-component glue supply system at a speed of 50cm/min (the glue injection frequency of the bi-component glue supply system is 1Hz, the glue injection amount is 100g each time, and the weight ratio of the material B to the material A is 1.5: 1), enabling the bi-component glue supply system to be fully soaked with mixed resin of the component AB, enabling the mixed resin to enter a mold (the three temperatures are 250 ℃, 150 ℃ and 100 ℃ respectively), and enabling the resin to be cured and molded at a high temperature and to leave the mold.
And (3) testing mechanical properties: testing the tensile strength, the tensile modulus, the elongation at break, the bending strength and the bending modulus of the prepared composite material according to the national standard GB/T16421-1996;
and (3) hydrolysis resistance test: the sample bars prepared according to the above standard are placed in a humid heat aging box with 85 ℃ and 85% humidity for 1000h, and then taken out to test the mechanical property and the reduction ratio of the sample bars.
Example 4
Preparation of the component B: weighing 50 kg of hydroxyl-terminated polybutadiene with the molecular weight of 1000g/mol and 50 kg of castor oil polyol, adding the mixture into a closed reaction kettle, heating to 120 ℃, stirring and vacuumizing, stopping vacuumizing and heating after 2h, cooling to 80 ℃, adding 91.5 kg of carbodiimide modified MDI (Kostew company) with the trade name of NPU (MX), and continuing to react for 2h to obtain the prepolymer with the NCO content of 22%.
Preparation of component A: 30 kg of polyester 2915 (Spathan corporation), 30 kg of polyester 3050 (Paston corporation), 18 kg of castor oil polyol, 5 kg of 550D mold release agent (Technick Products corporation), 4 kg of 3A activated molecular sieve which has been baked at high temperature, 0.2 kg of FOMREZ UL-28 as a catalyst, 0.8 kg of K-5218 as a 0.6 kg catalyst, 12 kg of talcum powder filler, 0.83 kg of ultraviolet ray absorbent benzotriazole and 0.66 kg of anti-aging agent dioctadecyl thiodipropionate are respectively weighed and added into a stirring kettle and stirred uniformly.
Respectively introducing the component A and the component B into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, enabling glass fibers to form a certain tension from a creel through a yarn guide plate under the drive of a tractor, enabling the glass fibers to pass through a glue injection box connected with the bi-component glue supply system (the glue injection frequency of the bi-component glue supply system is 1.6Hz, the glue injection amount is 180g each time, and the weight ratio of the material B to the material A is 1.08: 1) at a speed of 250cm/min, enabling the bi-component glue supply system to be fully soaked with mixed resin of the component AB, enabling the mixed resin to enter a mold (the three temperatures are respectively 200 ℃, 180 ℃ and 180 ℃), and enabling the resin to be cured and molded at a high temperature and to leave the mold.
And (3) testing mechanical properties: the prepared composite material is tested for tensile strength, tensile modulus, elongation at break, flexural strength and flexural modulus according to the national standard GB/T16421-1996.
And (3) hydrolysis resistance test: the sample bars prepared according to the above standard are placed in a humid heat aging box with 85 ℃ and 85% humidity for 1000h, and then taken out to test the mechanical property and the reduction ratio of the sample bars.
Comparative example 1
Commercially available polyether type two-component polyurethane pultrusion resin
Respectively introducing the component A and the component B into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, enabling glass fibers to form a certain tension from a creel through a yarn guide plate under the drive of a tractor, enabling the glass fibers to pass through a glue injection box connected with the bi-component glue supply system (the glue injection frequency of the bi-component glue supply system is 1.0Hz, the glue injection amount is 120g each time, and the weight ratio of the material B to the material A is 1.25: 1) at a speed of 150cm/min, enabling the glass fibers to be fully soaked with mixed resin of the component AB, enabling the mixed resin to enter a mold (the three temperatures are 160 ℃, 180 ℃ and 150 ℃ respectively), and enabling the resin to be cured and molded at a high temperature and to leave the mold.
And (3) testing mechanical properties: the prepared composite material is tested for tensile strength, tensile modulus, elongation at break, flexural strength and flexural modulus according to the national standard GB/T16421-1996.
And (3) hydrolysis resistance test: the sample bars prepared according to the above standard are placed in a humid heat aging box with 85 ℃ and 85% humidity for 1000h, and then taken out to test the mechanical property and the reduction ratio of the sample bars.
Comparative example 2
Commercially available polyester type two-component polyurethane pultrusion resin
Respectively introducing the component A and the component B into a storage tank A and a storage tank B corresponding to a bi-component glue supply system, enabling glass fibers to form a certain tension from a creel through a yarn guide plate under the drive of a tractor, enabling the glass fibers to pass through a glue injection box connected with the bi-component glue supply system (the glue injection frequency of the bi-component glue supply system is 1.0Hz, the glue injection amount is 120g each time, and the weight ratio of the material B to the material A is 1.05: 1) at a speed of 150cm/min, enabling the glass fibers to be fully soaked with mixed resin of the component AB, enabling the mixed resin to enter a mold (the three temperatures are 160 ℃, 180 ℃ and 150 ℃ respectively), and enabling the resin to be cured and molded at a high temperature and to leave the.
And (3) testing mechanical properties: the prepared composite material is tested for tensile strength, tensile modulus, elongation at break, flexural strength and flexural modulus according to the national standard GB/T16421-1996.
And (3) hydrolysis resistance test: the sample bars prepared according to the above standard are placed in a humid heat aging box with 85 ℃ and 85% humidity for 1000h, and then taken out to test the mechanical property and the reduction ratio of the sample bars.
Comparison of the performance data between the examples and the comparative examples:
as can be seen from the data in the table above:
comparative examples 1 to 4 the performance of the composite material prepared by using the commercially available polyester type two-component polyurethane pultrusion resin is basically equivalent to that of comparative example 2, and is obviously higher than that of comparative example 1 (the composite material prepared by using the commercially available polyether type two-component polyurethane pultrusion resin);
after hydrolysis tests, the performance retention rate of the examples 1-4 is obviously higher than that of the comparative example 2, and the performance retention ratio is equivalent to that of the comparative example 1.
The polyurethane composite material prepared by the invention has the mechanical strength of the polyester resin matrix composite material and the hydrolysis resistance of the polyether resin matrix composite material.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
Claims (7)
1. The preparation method of the hydrolysis-resistant polyurethane pultrusion resin composite material is characterized by comprising the following steps:
step S1, preparing a hydrolysis-resistant polyurethane prepolymer as the component B, vacuumizing the polyol with the hydrophobic function at 120 ℃ for 2 hours, cooling to 80 ℃, adding excessive carbodiimide modified isocyanate, and reacting for 2-3 hours to obtain the polyurethane prepolymer with-NCO content;
the polyol with the hydrophobic function in the step S1 is castor oil polyol or hydroxyl-terminated polybutadiene polyol with the molecular weight of 1000-2000 g/mol;
the NCO content of the prepolymer finally prepared in the step S1 is 15-27%;
step S2, preparing the A-component polyol crosslinking agent, wherein the A-component polyol crosslinking agent comprises the following components in parts by weight:
55-80 wt% of polyester polyol;
10-20 wt% of vegetable oil polyol;
2-8 wt% of a release agent;
2-5 wt% of a water removing agent;
0.2-1 wt% of a catalyst;
0-25 wt% of filler;
0.5-1 wt% of ultraviolet absorbent;
0.5-1 wt% of an anti-aging agent;
step S3, transferring the two components in the step S1 and the step S2 to 2 storage tanks of a bi-component glue supply system respectively;
and step S4, curing and molding the continuous fibers soaked with the resin through a segmented heating mold by a two-component polyurethane pultrusion system.
2. The method for preparing the hydrolysis-resistant polyurethane pultrusion resin composite material as claimed in claim 1, wherein the anti-aging agent is one of 2, 5-di-tert-butylhydroquinone or dioctadecyl thiodipropionate.
3. The method for preparing a hydrolysis-resistant polyurethane pultrusion resin composite material as claimed in claim 1, wherein the vegetable oil polyol in the step S2 is castor oil polyol; the water removing agent is a 3A activated molecular sieve, and is baked for more than 6 hours at 250 ℃ before use; the catalyst is a delayed type catalyst; the filler is one or a composition of more of calcium carbonate, aluminum hydroxide and talcum powder; the ultraviolet absorbent is one or a combination of a plurality of benzophenone or benzotriazole.
4. The preparation method of the hydrolysis-resistant polyurethane pultrusion resin composite material as claimed in claim 1, wherein the two-component glue supply system in the step S3 includes an A material tank, a B material tank, two metering pumps respectively connected below the AB material tank, and a static mixer module for mixing the AB material, the glue injection frequency is 0.2-2 Hz, and the glue injection amount is 50-200 g/time.
5. The method of preparing a hydrolysis-resistant polyurethane pultrusion resin composite material as claimed in claim 1, wherein the two-component polyurethane pultrusion system in the step S4 includes a creel, a yarn guide device, a glue injection box, a segmented heating mold and a tractor module; the glue supply system is connected with the glue injection box in a sealing mode, the segmented heating mold is heated in three zones, the temperature ranges of the two zones are 150-250 ℃, the temperature range of the third zone is room temperature-180 ℃, and the traction speed of the tractor is 10-280 cm/min.
6. The method for preparing a hydrolysis-resistant polyurethane pultrusion resin composite material as claimed in claim 1, wherein the step S4 includes the following four steps:
s401, mixing the material A and the material B which are ejected by the metering pump through a static mixer, and then feeding the mixture into a closed glue injection box of a two-component polyurethane pultrusion system;
s402, feeding the continuous fibers led out from the creel into a glue injection box under the driving of a tractor through a yarn guide device, and synchronously beating the resin in the glue injection box in the step S401 to fully mix and soak the resin;
s403, heating the front section and the middle section of the mold, and quickly curing the resin at 2/3 of the total length of the mold by the continuous fibers soaked by the resin under the combined action of temperature and a catalyst to form a composite material with strength;
and S404, slightly shrinking the resin while curing, and demolding at the tail section of the mold under the action of the release agent.
7. A hydrolysis-resistant polyurethane pultrusion resin composite material, which is characterized in that the polyurethane pultrusion resin composite material prepared by any one of the claims 1-6 is adopted.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1153997A1 (en) * | 2000-05-10 | 2001-11-14 | Rohm And Haas Company | Hot melt adhesive |
| CN102559126A (en) * | 2012-01-05 | 2012-07-11 | 北京天山新材料技术股份有限公司 | Hydrolysis-resistant double-component polyurethane adhesive for structure adhesion |
| CN102731989A (en) * | 2012-07-17 | 2012-10-17 | 上海珀理玫化学科技有限公司 | Composite material for pultrusion polyurethane resin and preparation method thereof |
| CN108250416A (en) * | 2017-12-29 | 2018-07-06 | 浙江华峰新材料股份有限公司 | Terminal hydroxy liquid modified rubber polyester polyol and its preparation method and application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1153997A1 (en) * | 2000-05-10 | 2001-11-14 | Rohm And Haas Company | Hot melt adhesive |
| CN102559126A (en) * | 2012-01-05 | 2012-07-11 | 北京天山新材料技术股份有限公司 | Hydrolysis-resistant double-component polyurethane adhesive for structure adhesion |
| CN102731989A (en) * | 2012-07-17 | 2012-10-17 | 上海珀理玫化学科技有限公司 | Composite material for pultrusion polyurethane resin and preparation method thereof |
| CN108250416A (en) * | 2017-12-29 | 2018-07-06 | 浙江华峰新材料股份有限公司 | Terminal hydroxy liquid modified rubber polyester polyol and its preparation method and application |
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