CN108250935B - Zero-solvent polyurethane sealing primer - Google Patents
Zero-solvent polyurethane sealing primer Download PDFInfo
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- CN108250935B CN108250935B CN201810026622.XA CN201810026622A CN108250935B CN 108250935 B CN108250935 B CN 108250935B CN 201810026622 A CN201810026622 A CN 201810026622A CN 108250935 B CN108250935 B CN 108250935B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a zero-solvent polyurethane closed primer and a preparation method thereof, belonging to the field of polyurethane. The primer disclosed by the invention comprises the following components or is prepared from the following components: polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a dispersant, an antioxidant auxiliary agent, MDI-50 and CDMDI-100L. Through reasonable material selection and proper proportion, the primer disclosed by the invention is a polyurethane primer which is solvent-free, completely meets the environmental protection requirement and has strong adhesive force.
Description
Technical Field
The invention relates to a synthetic method of a zero-solvent polyurethane closed primer, belonging to the field of polyurethane.
Technical Field
Polyurethanes, also known as polyurethanes, are a general term for macromolecular compounds containing repeating urethane groups in the backbone. Which are generally prepared by polymerizing organic diisocyanates or polyisocyanates with dihydroxy or polyhydroxy compounds. The polyurethane has wide application, for example, the polyurethane can replace rubber, plastic, nylon and the like, and is used for schools, airports, hotels, residential districts, landscaping and the like.
However, although polyurethane has high tensile strength by itself, when it is applied to a substrate whose bonding surface is hardly penetrated, for example: when cement-based materials, terrazzo materials, PVC substrates, etc. are used, the adhesive strength tends to be lower than the desired safety or structural level, and the polyurethane material often peels off from the substrate. Therefore, when the polyurethane is used for bonding a substrate with a difficult-to-permeate surface, the adhesion performance of the polyurethane and the substrate is improved by adopting a method of pre-coating a primer. The polyurethane primer is a polyurethane material which can seal moisture, mildew, alkali and the like of a base material and can be well adhered to the middle coating, wherein the primer plays a main role in adhesion and improves the adhesive force of the polyurethane and the base material.
The ideal primer performs the following functions: (1) protecting the basal plane (inhibiting the putrefaction of the basal body during the use process); (2) changing the surface chemical physical property of the matrix; (3) filling the pores on the surface of the substrate and reinforcing the surface weak area; (4) the base material is infiltrated into the interior of the base material to enhance the strength of the base material; (5) forming a coating film on the surface of the base material to inhibit the outward migration of water; (6) the product can be used indoors and outdoors without odor; (7) the product can be applied to cement base, terrazzo, PVC base materials and the like; and (8) epoxy, water-based epoxy, polyurethane, water-based polyurethane and other materials can be used as the primer upper layer.
The polymer (MDI-50 excessive) synthesized by polyether and diphenylmethane diisocyanate (MDI-50) can form a compact waterproof coating film, meets the condition of making a sealed bottom coating, but has difficult construction due to higher viscosity.
At present, most of polyurethane base coats are solvent-based products, the solvent content reaches 40-50%, and a large amount of organic solvent is volatilized into the atmosphere in the curing process of the base coats, so that the environment-friendly primer is inconsistent with the environmental protection policy advocated by the state, and the development of zero-solvent polyurethane base coats is urgently needed.
Disclosure of Invention
The inventor of the invention finds out through continuous efforts that the polyurethane primer which is solvent-free, completely meets the environmental protection requirement and has strong adhesive force can be prepared through reasonable material selection and proper proportion.
A first aspect of the invention provides a primer comprising or made from: polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a dispersant, an antioxidant auxiliary agent, MDI-50 and CDMDI-100L.
Optionally, the mass ratio of the polyether 3050 to the palm oil to the trimethylolpropane to the dispersant to the antioxidant auxiliary agent to the MDI-50 to the CDMDI-100L is 19-23:16-21:0.3-0.7:0.15-0.25:0.60-0.80:42-51: 10-13. More preferably, the mass ratio of the polyether 3050, the palm oil, the trimethylolpropane, the dispersant, the antioxidant auxiliary agent, the MDI-50 and the CDMDI-100L is 21.10:18.80:0.47:0.21:0.72:46.90: 11.80.
Preferably, the dispersant is a dispersant YB 201; the antioxidant additive is antioxidant additive B900; the MDI-50 is
MDI-50(
MDI-50 is a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate and is colorless to pink liquid at normal temperature); and/or the CDMDI-100L is
CDMDI-100L(
CDMDI-100L is carbodiimide modified 4,4' diphenyl methaneAlkane diisocyanate-MDI).
Further preferably, the components further comprise a mixture of calcium hydroxide and sodium sulfate, optionally the mass ratio of calcium hydroxide to sodium sulfate in the mixture is 1: 1. Most preferably, the mass ratio of the mixture to the polyether 3050 is 1-3: 19-23, preferably 2:21 or 2: 21.10.
The invention also provides a method for preparing the polyurethane primer, which comprises the following steps:
(a) adding polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a dispersing agent and an antioxidant auxiliary agent into a reaction kettle, and vacuumizing for 2 hours at 120 ℃ and-0.09 MPA;
(b) cooling to 60 ℃, adding MDI-50 and CDMDI-100L, stirring for 30 minutes, heating to 75-80 ℃, and keeping reacting for 2 hours; and
(c) when the NCO content is 17.5% -18%, cooling to 60 ℃, and then filtering out the reaction kettle.
Optionally, in the method for preparing a polyurethane primer of the present invention, the mass ratio of the polyether 3050, the palm oil, the trimethylolpropane, the dispersant, the antioxidant aid, the MDI-50 and the CDMDI-100L is 19-23:16-21:0.3-0.7:0.15-0.25:0.60-0.80:42-51: 10-13. More preferably, the mass ratio of the polyether 3050, the palm oil, the trimethylolpropane, the dispersant, the antioxidant auxiliary agent, the MDI-50 and the CDMDI-100L is 21.10:18.80:0.47:0.21:0.72:46.90: 11.80.
Preferably, in the method for preparing the polyurethane primer of the invention, the dispersant is dispersant YB 201; the antioxidant additive is antioxidant additive B900; the MDI-50 is
MDI-50(
MDI-50 is a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate and is colorless to pink liquid at normal temperature); and/or the CDMDI-100L is
CDMDI-100L(
CDMDI-100L is carbodiimide modified 4,4' diphenylmethane diisocyanate-MDI).
Further preferably, in the method for preparing a polyurethane primer according to the present invention, the components further include a mixture of calcium hydroxide and sodium sulfate, optionally, the mass ratio of calcium hydroxide to sodium sulfate in the mixture is 1: 1. Most preferably, the mass ratio of the mixture to the polyether 3050 is 1-3: 19-23, preferably 2:21 or 2: 21.10.
The invention also provides the use of a mixture of calcium hydroxide and sodium sulfate in the preparation of a polyurethane primer. Optionally, the mass ratio of the calcium hydroxide to the sodium sulfate is 1-2:2-1, preferably 1:1, and further preferably, the mixture accounts for 1.5-2.4%, preferably 1.9-2.2% of the total mass of the primer formulation
The polyurethane provided by the invention has excellent adhesion and permeability, environmental protection and the like.
The invention will be explained in more detail below by means of the following examples. The following examples are illustrative only, and it should be understood that the present invention is not limited by the following examples.
Example 1
The formula and the processing technology of the product are as follows:
product formula
| Name of raw materials | Polyether 3050 | Palm oil | Trimethylolpropane | Dispersant YB201 | Antioxidant auxiliary B900 | MDI-50 | CDMDI-100L |
| Quality (Kg) | 21.10 | 18.80 | 0.47 | 0.21 | 0.72 | 46.90 | 11.80 |
The product process comprises the following steps:
1. adding polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a dispersant YB201 and an antioxidant additive B900 into a reaction kettle, and vacuumizing for 2 hours at 120 ℃ and-0.09 MPA;
2. cooling to 60 deg.C, adding
MDI-50(
MDI-50 is a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, and is colorless to pink liquid at normal temperature) and
CDMDI-100L(
CDMDI-100L is carbodiimide modified 4,4' -diphenylmethane diisocyanate-MDI), stirring for 30 minutes, heating to 75-80 ℃, and keeping reacting for 2 hours;
3. when the NCO content is 17.5% -18%, cooling to 60 ℃, and then filtering out the reaction kettle.
Physical Properties
| Time to surface dry | Actual drying time | Adhesion force | Permeability of |
| 4 hours | 8 hours | 4.5MPA | Is excellent in |
Note: the adhesion test method is described in GB/T9286-1998; permeability testing is described in GB/T18851.12008 (same below)
Chemical properties
Example 2
The formula and the processing technology of the product are as follows:
product formula
| Name of raw materials | Polyether 3050 | Palm oil | Trimethylolpropane | Dispersant YB201 | Antioxidant auxiliary B900 | MDI-50 | CDMDI-100L |
| Quality (Kg) | 19.00 | 16.00 | 0.30 | 0.15 | 0.60 | 42.00 | 10.00 |
The product process comprises the following steps:
1. adding polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a dispersant YB201 and an antioxidant additive B900 into a reaction kettle, and vacuumizing for 2 hours at 120 ℃ and-0.09 MPA;
2. cooling to 60 deg.C, adding
MDI-50(
MDI-50 is a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, and is colorless to pink liquid at normal temperature) and
CDMDI-100L(
CDMDI-100L is carbodiimide modified 4,4' -diphenylmethane diisocyanate-MDI), stirring for 30 minutes, heating to 75-80 ℃, and keeping reacting for 2 hours;
3. when the NCO content is 17.5% -18%, cooling to 60 ℃, and then filtering out the reaction kettle.
Physical Properties
| Time to surface dry | Actual drying time | Adhesion force | Permeability of |
| 4.2 hours | 9 hours | 4.9MPA | Is excellent in |
Chemical properties
Example 3
The formula and the processing technology of the product are as follows:
product formula
| Name of raw materials | Polyether 3050 | Palm oil | Trimethylolpropane | Dispersant YB201 | Antioxidant auxiliary B900 | MDI-50 | CDMDI-100L |
| Quality (Kg) | 23.00 | 21.00 | 0.70 | 0.25 | 0.80 | 51.00 | 13.00 |
The product process comprises the following steps:
1. adding polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a dispersant YB201 and an antioxidant additive B900 into a reaction kettle, and vacuumizing for 2 hours at 120 ℃ and-0.09 MPA;
2. cooling to 60 deg.C, adding
MDI-50(
MDI-50 is a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, and is colorless to pink liquid at normal temperature) and
CDMDI-100L(
CDMDI-100L is carbodiimide modified 4,4' -diphenylmethane diisocyanate-MDI), stirring for 30 minutes, heating to 75-80 ℃, and keeping reacting for 2 hours;
3. when the NCO content is 17.5% -18%, cooling to 60 ℃, and then filtering out the reaction kettle.
Physical Properties
| Time to surface dry | Actual drying time | Adhesion force | Permeability of |
| 4.1 hours | 8.5 hours | 4.6MPA | Is excellent in |
Chemical properties
Example 4
The formula and the processing technology of the product are as follows:
product formula
The product process comprises the following steps:
1. adding polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a mixture of calcium hydroxide and sodium sulfate, a dispersant YB201 and an antioxidant additive B900 into a reaction kettle, and vacuumizing for 2 hours at 120 ℃ and-0.09 MPA;
2. cooling to 60 deg.C, adding
MDI-50(
MDI-50 is a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, and is colorless to pink liquid at normal temperature) and
CDMDI-100L(
CDMDI-100L is carbodiimide modified 4,4' -diphenylmethane diisocyanate-MDI), stirring for 30 minutes, heating to 75-80 ℃, and keeping reacting for 2 hours;
3. when the NCO content is 17.5% -18%, cooling to 60 ℃, and then filtering out the reaction kettle.
Physical Properties
| Time to surface dry | Actual drying time | Adhesion force | Permeability of |
| 3.5 hours | 7 hours | 6.0MPA | Is excellent in |
Chemical properties
Example 5
The formula and the processing technology of the product are as follows:
product formula
The product process comprises the following steps:
1. adding polyether 3050 (polyoxypropylene ether triol 3050), palm oil, trimethylolpropane, a mixture of calcium hydroxide and sodium sulfate, a dispersant YB201 and an antioxidant additive B900 into a reaction kettle, and vacuumizing for 2 hours at 120 ℃ and-0.09 MPA;
2. cooling to 60 deg.C, adding
MDI-50(
MDI-50 is a mixture of 2,4 '-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate, and is colorless to pink liquid at normal temperature) and
CDMDI-100L(
CDMDI-100L is carbodiimide modified 4,4' -diphenylmethane diisocyanate-MDI), stirring for 30 minutes, heating to 75-80 ℃, and keeping reacting for 2 hours;
3. when the NCO content is 17.5% -18%, cooling to 60 ℃, and then filtering out the reaction kettle.
Physical Properties
| Time to surface dry | Actual drying time | Adhesion force | Permeability of |
| 3.6 hours | 7.1 hours | 6.5MPA | Is excellent in |
Chemical properties
Although the present invention has been described in the above-mentioned embodiments, it is to be understood that the present invention may be further modified and changed without departing from the spirit of the present invention, and that such modifications and changes are within the scope of the present invention.
Claims (6)
1. A primer comprising the following components: polyether 3050, palm oil, trimethylolpropane, a dispersant, an antioxidant auxiliary agent, MDI-50, CDMDI-100L, calcium hydroxide and sodium sulfate,
wherein: the mass ratio of the polyether 3050 to the palm oil to the trimethylolpropane to the dispersant to the antioxidant auxiliary agent to the MDI-50 to the CDMDI-100L is 19-23:16-21:0.3-0.7:0.15-0.25:0.60-0.80:42-51: 10-13;
the mass ratio of the calcium hydroxide to the sodium sulfate is 1: 1;
the mass ratio of the sum of the mass of the calcium hydroxide and the mass of the sodium sulfate to the mass of the polyether 3050 is 1-3: 19-23.
2. The primer according to claim 1, wherein the mass ratio of the polyether 3050, the palm oil, the trimethylolpropane, the dispersant, the antioxidant aid, the MDI-50 and the CDMDI-100L is 21.10:18.80:0.47:0.21:0.72:46.90: 11.80.
3. The primer according to claim 2 wherein the dispersant is dispersant YB 201; the antioxidant additive is antioxidant additive B900; the MDI-50 is
MDI-50; the CDMDI-100L is
CDMDI-100L。
4. The primer according to any one of claims 1 to 3, wherein the mass ratio of the sum of the masses of the calcium hydroxide and the sodium sulfate to the polyether 3050 is 2:21 or 2: 21.10.
5. A process for preparing the primer of claim 1, comprising the steps of:
(a) adding polyether 3050, palm oil, trimethylolpropane, a dispersing agent, an antioxidant auxiliary agent, calcium hydroxide and sodium sulfate into a reaction kettle, and vacuumizing for 2 hours at 120 ℃ and-0.09 MPa;
(b) cooling to 60 ℃, adding MDI-50 and CDMDI-100L, stirring for 30 minutes, heating to 75-80 ℃, and keeping reacting for 2 hours;
(c) when the NCO content is 17.5-18%, cooling to 60 ℃, then filtering out the reaction kettle,
wherein the mass ratio of the polyether 3050 to the palm oil to the trimethylolpropane to the dispersant to the antioxidant auxiliary agent to the MDI-50 to the CDMDI-100L is 19-23:16-21:0.3-0.7:0.15-0.25:0.60-0.80:42-51: 10-13.
6. The method of claim 5, wherein the mass ratio of the polyether 3050, palm oil, trimethylolpropane, dispersant, antioxidant aid, MDI-50, and CDMDI-100L is 21.10:18.80:0.47:0.21:0.72:46.90: 11.80.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810026622.XA CN108250935B (en) | 2018-01-11 | 2018-01-11 | Zero-solvent polyurethane sealing primer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810026622.XA CN108250935B (en) | 2018-01-11 | 2018-01-11 | Zero-solvent polyurethane sealing primer |
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| CN108250935A CN108250935A (en) | 2018-07-06 |
| CN108250935B true CN108250935B (en) | 2020-10-09 |
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| CN112812732A (en) * | 2021-02-01 | 2021-05-18 | 山东华诚高科胶粘剂有限公司 | Two-component polyurethane adhesive and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280167A (en) * | 2007-04-02 | 2008-10-08 | 上海康达化工有限公司 | Solvent-free polyurethane laminating adhesive for normal temperature coating, preparation and use thereof |
| CN103665315A (en) * | 2013-11-21 | 2014-03-26 | 珠海长先化学科技有限公司 | Synthesis method of modified polyurethane resin for circuit board |
| CN103980810A (en) * | 2014-05-19 | 2014-08-13 | 上海正欧实业有限公司 | Waterproof solvent-free single-component polyurethane lacquer used on wet surface and preparation method thereof |
| CN105176475A (en) * | 2015-09-16 | 2015-12-23 | 湖州倍格曼新材料股份有限公司 | Solvent-free polyurethane adhesive with high initial viscosity and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10043433A1 (en) * | 2000-09-04 | 2002-03-21 | Bayer Ag | Aqueous 2-component PUR systems |
| US20080207811A1 (en) * | 2007-02-28 | 2008-08-28 | Brust Thomas B | Pigment based inks for high speed durable inkjet printing |
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- 2018-01-11 CN CN201810026622.XA patent/CN108250935B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280167A (en) * | 2007-04-02 | 2008-10-08 | 上海康达化工有限公司 | Solvent-free polyurethane laminating adhesive for normal temperature coating, preparation and use thereof |
| CN103665315A (en) * | 2013-11-21 | 2014-03-26 | 珠海长先化学科技有限公司 | Synthesis method of modified polyurethane resin for circuit board |
| CN103980810A (en) * | 2014-05-19 | 2014-08-13 | 上海正欧实业有限公司 | Waterproof solvent-free single-component polyurethane lacquer used on wet surface and preparation method thereof |
| CN105176475A (en) * | 2015-09-16 | 2015-12-23 | 湖州倍格曼新材料股份有限公司 | Solvent-free polyurethane adhesive with high initial viscosity and preparation method thereof |
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