CN113388074A - Polyurethane resin system and preparation method thereof - Google Patents
Polyurethane resin system and preparation method thereof Download PDFInfo
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- CN113388074A CN113388074A CN202110639816.9A CN202110639816A CN113388074A CN 113388074 A CN113388074 A CN 113388074A CN 202110639816 A CN202110639816 A CN 202110639816A CN 113388074 A CN113388074 A CN 113388074A
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- polyurethane resin
- resin system
- polyol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
Abstract
The invention relates to the field of polyurethane, and more specifically relates to a polyurethane resin system and a preparation method thereof, wherein the preparation raw materials of the polyurethane resin system comprise organic polyol, acrylate monomer, catalyst, isocyanate and initiation aid, the viscosity of the polyurethane resin system at 25 ℃ is 20-300mPa.s, preferably 60-90mPa.s, and the time for increasing the viscosity of 175g of the polyurethane resin system to 500mPa.s in a water bath at 30 ℃ is 50-200min, preferably 70-110 min. The viscosity of the polyurethane resin system at 25 ℃ is lower than 100mPa.s, the time for increasing the viscosity of the polyurethane resin system of 175g to 500mPa.s at 30 ℃ is longer than 60min, the polyurethane resin system has higher thermal deformation temperature of a casting body, the thermal deformation temperature of the casting body is higher than 60 ℃, and the polyurethane resin system has low exothermicity and high strength and can be widely applied to preparation of composite products of winding, pultrusion and pouring processes which need long operation period and have higher strength requirements.
Description
Technical Field
The invention relates to the field of polyurethane, in particular to a polyurethane resin system and a preparation method thereof.
Background
Polyurethane is a high molecular compound, has the characteristics of rapid reaction and moderate tensile strength, is widely applied to composite products with larger sizes along with the development of polyurethane resin at present, and comprises composite pipelines and telegraph poles in a winding production process, composite grids and bridge supports in a pultrusion production process, automobile engine covers and wind-electricity blades in a vacuum infusion process and the like. The production of large-size composite products requires a longer operable time for a polyurethane resin system to ensure that fiber reinforced materials such as glass fibers and carbon fibers have better wettability in the production process to achieve higher composite performance. However, the operable time (the time for increasing the viscosity to 500mpa.s at 175g 30 ℃) of the conventional polyurethane resin system cannot be more than 50min, and the thermal deformation temperature of the casting body is generally lower than 60 ℃, so that a large-size composite product with the thickness of more than 5 cm and more than 10m cannot be prepared.
Therefore, there is a need to provide a polyurethane resin system having a workable time (time to increase the viscosity to 500mpa.s at 175g 30 ℃) of greater than 60min and a casting body thermal deformation temperature of generally greater than 60 ℃.
Disclosure of Invention
In view of the problems in the prior art, the first aspect of the present invention provides a polyurethane resin system, which is prepared from one or more organic polyols, at least one acrylate monomer, isocyanate, an initiation aid, at least one compound represented by formula (1);
As a preferred technical scheme of the invention, the viscosity of the polyurethane resin system at 25 ℃ is 20-300mPa.s, preferably 60-90mPa.s, and the time for increasing the viscosity of 175g of the polyurethane resin system to 500mPa.s under a water bath at 30 ℃ is 50-200min, preferably 70-110 min.
As a preferable technical scheme of the invention, the structure of the acrylate monomer is shown as a formula (2);
In a preferred embodiment of the present invention, the polyurethane system further comprises a catalyst.
As a preferred embodiment of the present invention, the organic polyol, the compound represented by the formula (1), the acrylate monomer, and the catalyst have a mixed viscosity of 10 to 200mPa.s at 25 ℃ and a hydroxyl value of 200-600mg KOH/g.
As a preferred embodiment of the present invention, the mixing viscosity of the isocyanate and the initiation aid is 50 to 500cps at 25 ℃.
As a preferred embodiment of the present invention, the hydroxyl value of the organic polyol is 100-700 mgKOH/g.
In a preferred embodiment of the present invention, the organic polyol has a functionality of 2 to 4.
As a preferred embodiment of the present invention, the organic polyol is one or more selected from the group consisting of polyether polyol, polyester polyol, polyether ester polyol, polymer polyol, polycarbonate polyol and polyether carbonate polyol.
In a preferred embodiment of the present invention, the isocyanate group content of the isocyanate is 28 to 35 wt%.
The second aspect of the present invention provides a method for preparing the polyurethane resin system, comprising: mixing the preparation raw materials of the polyurethane resin system to obtain the polyurethane resin.
Compared with the prior art, the invention has the following beneficial effects:
the viscosity of the polyurethane resin system at 25 ℃ is lower than 100mPa.s, the time for increasing the viscosity of the polyurethane resin system of 175g to 500mPa.s at 30 ℃ is longer than 60min, the polyurethane resin system has higher thermal deformation temperature of a casting body, the thermal deformation temperature of the casting body is higher than 60 ℃, and the polyurethane resin system has low exothermicity and high strength and can be widely applied to preparation of composite products of winding, pultrusion and pouring processes which need long operation period and have higher strength requirements. Meanwhile, the defects of the vacuum resin infusion system technology in the prior art can be overcome, and the production quality and the production efficiency of the wind power blade can be improved.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a polyurethane resin system, which is prepared from one or more organic polyols, at least one acrylate monomer, isocyanate, an initiation aid and a compound shown as a formula (1);
In one embodiment, the polyurethane resin system has a viscosity of 20 to 300mpa.s, preferably 60 to 90mpa.s at 25 ℃ and the time for 175g of the polyurethane resin system to increase to 500mpa.s in a water bath at 30 ℃ is 50 to 200min, preferably 70 to 110 min.
This applicationPlease note C2-12Examples of the aliphatic alkyl group include a methyl group, an ethyl group, an n-propyl group, an isobutyl group, a sec-butyl group, a 3-pentyl group, a 2- (2-methyl) butyl group, a neopentyl group, a 2- (2-methyl) pentyl group, and a hydroxymethyl group.
Examples of the substituted or unsubstituted aromatic group in the present application include tolyl, phenyl, phenol, naphthyl, hydroxytoluene, phenylthio and the like.
Preferably, n is 1.
Preferably, R1 is a substituted or unsubstituted alicyclic group.
In one embodiment, the compound of formula (1) is allyl cyclohexylhexanoate.
In one embodiment, the organic polyol has a functionality of 2 to 4.
Preferably, the organic polyol is selected from one or more of polyether polyol, polyester polyol, polyether ester polyol, polymer polyol, polycarbonate polyol and polyether carbonate polyol.
Polymer polyol: the polymer polyol, also called vinyl polymer graft polyether polyol, POP for short, is generally white or light opalescent in appearance, is a polyol containing an organic filler, can replace an inorganic filler, not only enables polyurethane foam to have higher bearing capacity and good resilience, but also enables the foam cell structure and physical and mechanical properties to be improved.
Functionality: the polymer functionality, the average number of reactive functional groups present on the polymer chain, is referred to as the functionality or average functionality of the polymer. Common active groups are hydroxyl-OH, carboxyl-COOH, allyl chloride, amino (amino) -NH2, and the like.
Preferably, the organic polyol is (a) a polyether polyol having a functionality of 2 and (b) an organic polyol having a functionality of 3.
Preferably, the weight ratio of (a) polyether polyol having a functionality of 2 to (b) organic polyol having a functionality of 3 is 1: (0.3-2).
The (a) polyether polyol having a functionality of 2 and (b) organic polyol having a functionality of 3 described herein are not particularly limited and may be selected by those skilled in the art in accordance with the description herein.
The polyether polyol (a) having a functionality of 2 may be exemplified by uranol D204, Puranol D210, Puranol D220, Puranol D230, Puranol D240, Puranol D280 and Lupranol 1200.
The organic polyol having a functionality of 3 (b) may be exemplified by Puranol G303, Puranol G303F, Puranol G305, Puranol G306, Puranol G307, Puranol G310, Puranol G4030, Puranol G5030, Voranol CP 455, and the like.
In one embodiment, the hydroxyl value of the organic polyol is 100-700mgKOH/g, preferably 280-360 mgKOH/g.
In one embodiment, the acrylate monomer has a structure represented by formula (2);
In one embodiment, the hydroxyl number of the acrylate monomer is 390-410mg KOH/g, preferably 396mg KOH/g.
Preferably, the acrylate monomer is hydroxypropyl methacrylate.
In the prior art, in order to improve the operable time, some viscosity reducers such as dioctyl phthalate, dioctyl terephthalate, butyl benzyl phthalate and the like are often added, however, the addition of the viscosity reducers influences the crosslinking between the polyol and the isocyanate to a certain extent, the applicant unexpectedly discovers that when the alkenyl ester compound of the compound shown as the formula (1) and the acrylate monomer with a specific weight ratio are added, particularly the compound shown as the formula (1) is allyl cyclohexyl hexanoate, the acrylate monomer is hydroxypropyl methacrylate, the viscosity of the component A is 10-200mPa.s and the hydroxyl value is 250-400mg KOH/g through the matching of the contents of the components, the operable time of the polyurethane resin system after the reaction between the component A and the component B is not less than 70min, and the applicant thinks that the possible reason is that, on the one hand, the cyclohexyl structure in the cyclohexyl allyl hexanoate increases the resistance of the interaction between molecules, and reduces the reaction rate when the A component and the B component are mixed, and on the other hand, the hydroxypropyl methacrylate plays a role in inhibiting the reaction of the organic polyol and the isocyanate in the application.
In one embodiment, the polyurethane system further comprises a catalyst.
The catalyst described in the present application is not particularly limited and may be conventionally selected by those skilled in the art.
In one embodiment, the catalyst is copper naphthenate.
In one embodiment, the organic polyol, the compound represented by formula (1), the acrylate monomer, and the catalyst have a mixed viscosity of 10 to 200mPa.s at 25 ℃ and a hydroxyl value of 200-600mg KOH/g.
Preferably, the organic polyol, the compound represented by the formula (1), the acrylate monomer and the catalyst have a hydroxyl value of 250-400mg KOH/g.
In one embodiment, the weight ratio of the compound represented by formula (1) to the organic polyol is 1: (6-12).
In one embodiment, the weight ratio of acrylate monomer to organic polyol is 1: (1.7-2).
In one embodiment, the catalyst comprises 0.05 to 0.2 wt% of the total amount of the organic polyol and the acrylate monomer.
In one embodiment, the isocyanate group content of the isocyanate is 28 to 35 weight percent.
Preferably, the isocyanate group content of the isocyanate is 31.5 wt%.
In one embodiment, the isocyanate is a polyisocyanate.
The type of polyisocyanate described herein is not particularly limited and can be selected by those skilled in the art in accordance with the description herein.
The initiation aids described herein are not particularly limited and can be routinely selected by those skilled in the art.
In one embodiment, the initiation aid is dibenzoyl peroxide.
In one embodiment, the isocyanate and the initiation aid have a mixed viscosity of 50 to 500cps at 25 ℃.
In one embodiment, the weight ratio of isocyanate to initiation aid is (47.5-50): 1.
in one embodiment, the ratio of the total weight of the organic polyol, acrylate monomer, catalyst, compound of formula (1) to the total weight of isocyanate and initiation aid is 100: (60-90).
In one embodiment, the polyurethane resin system further comprises a crosslinker.
The content and kind of the crosslinking agent described herein are not particularly limited and may be conventionally selected by those skilled in the art.
In one embodiment, the cross-linking agent is triethanolamine.
The second aspect of the present invention provides a method for preparing the polyurethane resin system: the method comprises the following steps: mixing the preparation raw materials of the polyurethane resin system to obtain the polyurethane resin.
The raw materials for the preparation of the polyurethane resin systems described in this application can be divided into two components, three components, four components, five components, etc., which can be routinely selected by the person skilled in the art.
In one embodiment, the polyurethane resin system is prepared from raw materials including an a-component and a B-component.
In one embodiment, the A component comprises organic polyol, acrylate monomer, catalyst, crosslinking agent, and compound shown in formula (1).
The component A described herein is colorless or yellowish in appearance, and different colorants may be added to change the color, its viscosity being from 10 to 200mPa.s and its hydroxyl value being from 200 to 600mg KOH/g.
Preferably, the hydroxyl value of the component A is 250-400mg KOH/g.
In one embodiment, the B component includes an isocyanate and an initiation aid.
The B component has a light yellow to dark brown appearance, different colorants may be added to change color, and a viscosity of 50 to 500 cps.
In one embodiment, the weight ratio of the a component to the B component is 100: (60-90).
In one embodiment, the method of preparing the polyurethane resin system comprises the steps of:
(1) preparation of a component A: putting organic polyol, a compound shown as a formula (1), an acrylate monomer, a catalyst and a crosslinking agent into a reaction kettle, and uniformly stirring;
(2) b, preparation of a component: adding isocyanate and an initiation auxiliary agent into the other reaction kettle, and uniformly stirring;
(3) mixing the component A and the component B to obtain the composition.
The component A and the component B in the polyurethane resin system are packaged separately.
Those skilled in the art who have not disclosed this application may make routine selections.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, but it should be understood that these examples are merely illustrative and not restrictive. The starting materials used in the examples which follow are all commercially available unless otherwise stated.
Examples 1 to 5
Examples 1-5 of the present invention each provide a polyurethane resin system having the specific composition shown in Table 1 in parts by weight.
TABLE 1
In Table 1 (a) a polyether polyol having a functionality of 2 is available from Basf under the designation Lupranol 1200, (b) an organic polyol having a functionality of 3 is available from Dow under the designation Voranol CP 455, and an isocyanate is available from Dow under the designation Voracor CL 100.
The preparation method of the polyurethane resin system comprises the following steps:
(1) adding each raw material in the component A into a reaction kettle, starting a stirrer, and uniformly mixing;
(2) adding each raw material in the component B into another reaction kettle, starting a stirrer, and uniformly mixing;
(3) mixing the component A and the component B.
Performance evaluation
The polyurethane resin systems obtained in examples 1 to 5 were each tested, and the test results are shown in Table 2.
TABLE 2
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A polyurethane resin system is characterized in that the preparation raw materials comprise one or more organic polyols, at least one acrylate monomer, isocyanate, an initiation aid and at least one compound shown as a formula (1);
(1) wherein n is any integer of 1-5; r1 is selected from substituted or unsubstituted C2-12Aliphatic alkyl group, substituted or unsubstituted alicyclic groupAnd substituted or unsubstituted aromatic groups and derivatives thereof.
2. The polyurethane resin system according to claim 1, wherein the acrylate monomer has a structure represented by formula (2);
(2) wherein R2 is selected from substituted or unsubstituted C2-4Any of the aliphatic group, substituted or unsubstituted alicyclic group, and substituted or unsubstituted aromatic group of (a); r3 is hydrogen, substituted or unsubstituted C2-4Any of (1) alkyl groups.
3. The polyurethane resin system of claim 1, wherein the organic polyol is selected from one or more of polyether polyol, polyester polyol, polyether ester polyol, polymer polyol, polycarbonate polyol, polyether carbonate polyol.
4. The polyurethane resin system as claimed in claim 3, wherein the hydroxyl value of the organic polyol is 100-700 mgKOH/g.
5. The polyurethane resin system of claim 4, wherein the organic polyol has a functionality of 2 to 4.
6. The polyurethane resin system of claim 1, wherein the polyurethane system further comprises a catalyst.
7. The polyurethane resin system as claimed in claim 6, wherein the organic polyol, the compound represented by formula (1), the acrylate monomer, and the catalyst have a mixed viscosity of 10 to 200mPa.s at 25 ℃, a hydroxyl value of 200-600mg KOH/g, and a weight of the mixture is 55 to 70 wt% based on the total weight.
8. The polyurethane resin system as claimed in claim 1, wherein the isocyanate group content of the isocyanate is 28 to 35 wt%.
9. The polyurethane resin system according to claim 1, wherein the viscosity of the polyurethane resin system at 25 ℃ is 20-300mpa.s, preferably 60-90mpa.s, and the time for increasing the viscosity of 175g of the polyurethane resin system to 500mpa.s in a water bath at 30 ℃ is 50-200min, preferably 70-110 min.
10. A method of preparing a polyurethane resin system according to any one of claims 1-9: it is characterized by comprising: mixing the preparation raw materials of the polyurethane resin system to obtain the polyurethane resin.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110639816.9A CN113388074A (en) | 2021-06-08 | 2021-06-08 | Polyurethane resin system and preparation method thereof |
| CN202111216821.5A CN113788916A (en) | 2021-06-08 | 2021-10-19 | Polyurethane resin and preparation method thereof |
| PCT/CN2021/124692 WO2022257317A1 (en) | 2021-06-08 | 2021-10-19 | Polyurethane resin and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110639816.9A CN113388074A (en) | 2021-06-08 | 2021-06-08 | Polyurethane resin system and preparation method thereof |
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| Publication Number | Publication Date |
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| CN113388074A true CN113388074A (en) | 2021-09-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110639816.9A Pending CN113388074A (en) | 2021-06-08 | 2021-06-08 | Polyurethane resin system and preparation method thereof |
| CN202111216821.5A Pending CN113788916A (en) | 2021-06-08 | 2021-10-19 | Polyurethane resin and preparation method thereof |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202111216821.5A Pending CN113788916A (en) | 2021-06-08 | 2021-10-19 | Polyurethane resin and preparation method thereof |
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| CN (2) | CN113388074A (en) |
| WO (1) | WO2022257317A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788916A (en) * | 2021-06-08 | 2021-12-14 | 道生天合材料科技(上海)股份有限公司 | Polyurethane resin and preparation method thereof |
| CN115181235A (en) * | 2022-06-14 | 2022-10-14 | 苏州贝彩纳米科技有限公司 | PPC-based polyurethane sound insulation and noise reduction material and preparation method thereof |
| WO2023142013A1 (en) * | 2022-01-29 | 2023-08-03 | Henkel Ag & Co. Kgaa | Two-part polyurethane- (meth) acrylic hybrid adhesive composition |
| CN115181235B (en) * | 2022-06-14 | 2024-04-19 | 苏州贝彩纳米科技有限公司 | PPC-based polyurethane sound insulation and noise reduction material and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4322242A1 (en) * | 1993-07-03 | 1995-01-12 | Basf Lacke & Farben | Aqueous two-component polyurethane coating composition, process for its preparation and its use in processes for the production of a multi-layer coating |
| NL1017840C2 (en) * | 2001-04-12 | 2002-10-15 | Dsm Nv | LPA hybrid. |
| CN104974502B (en) * | 2014-04-10 | 2019-12-27 | 科思创德国股份有限公司 | Polyurethane composite material and preparation method thereof |
| CN105778005B (en) * | 2014-12-01 | 2020-04-28 | 科思创德国股份有限公司 | Free-radically polymerizable polyurethane composition |
| WO2019051637A1 (en) * | 2017-09-12 | 2019-03-21 | Covestro Deutschland Ag | Composite material comprising a polyurethane-polyacrylate resin matrix |
| CN111825822A (en) * | 2019-04-15 | 2020-10-27 | 科思创德国股份有限公司 | Method for storing isocyanate reactive component |
| CN110372823A (en) * | 2019-07-12 | 2019-10-25 | 万华化学集团股份有限公司 | A kind of single-component thermosetting polyurethane combined material |
| CN113444223A (en) * | 2020-03-26 | 2021-09-28 | 科思创德国股份有限公司 | Polyol formulation and polyurethane resin |
| CN113388074A (en) * | 2021-06-08 | 2021-09-14 | 道生天合材料科技(上海)股份有限公司 | Polyurethane resin system and preparation method thereof |
-
2021
- 2021-06-08 CN CN202110639816.9A patent/CN113388074A/en active Pending
- 2021-10-19 CN CN202111216821.5A patent/CN113788916A/en active Pending
- 2021-10-19 WO PCT/CN2021/124692 patent/WO2022257317A1/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788916A (en) * | 2021-06-08 | 2021-12-14 | 道生天合材料科技(上海)股份有限公司 | Polyurethane resin and preparation method thereof |
| WO2022257317A1 (en) * | 2021-06-08 | 2022-12-15 | 道生天合材料科技(上海)股份有限公司 | Polyurethane resin and preparation method therefor |
| WO2023142013A1 (en) * | 2022-01-29 | 2023-08-03 | Henkel Ag & Co. Kgaa | Two-part polyurethane- (meth) acrylic hybrid adhesive composition |
| CN115181235A (en) * | 2022-06-14 | 2022-10-14 | 苏州贝彩纳米科技有限公司 | PPC-based polyurethane sound insulation and noise reduction material and preparation method thereof |
| CN115181235B (en) * | 2022-06-14 | 2024-04-19 | 苏州贝彩纳米科技有限公司 | PPC-based polyurethane sound insulation and noise reduction material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113788916A (en) | 2021-12-14 |
| WO2022257317A1 (en) | 2022-12-15 |
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Application publication date: 20210914 |