CN106117451A - A kind of preparation method of acrylic ester grafted modified aqueous polyurethane resin - Google Patents
A kind of preparation method of acrylic ester grafted modified aqueous polyurethane resin Download PDFInfo
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- CN106117451A CN106117451A CN201610607021.9A CN201610607021A CN106117451A CN 106117451 A CN106117451 A CN 106117451A CN 201610607021 A CN201610607021 A CN 201610607021A CN 106117451 A CN106117451 A CN 106117451A
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- Prior art keywords
- aqueous polyurethane
- polyurethane resin
- acrylic
- modified aqueous
- acrylic ester
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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
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (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)
Abstract
The invention discloses the preparation method of a kind of acrylic ester grafted modified aqueous polyurethane resin, comprise the following steps: first by PEPA Novomer vacuum dehydration, drip diisocyanate after being passed through nitrogen, reaction obtains base polyurethane prepolymer for use as I；Then multi-hydroxy carboxy acid being joined in base polyurethane prepolymer for use as I, then drip glycol monomer, reaction obtains base polyurethane prepolymer for use as；Again toward base polyurethane prepolymer for use as
Description
Technical field
The present invention relates to the preparation method of a kind of waterborne polyurethane resin, especially relate to a kind of acrylic ester grafted modification
The preparation method of waterborne polyurethane resin.
Background technology
Aqueous polyurethane odorlessness, Diamond Search, energy-conserving and environment-protective, easy to operate, there is outstanding physico-chemical property simultaneously, such as: change
Learn stability, rub resistance, toughness, elasticity, be widely used for the covering with paint of the base materials such as plastics, timber, metal as coating, and
And application is also constantly expanding.But aqueous polyurethane there is also resistance to water, solvent resistance, chemical-resistant and machinery
The shortcoming of the poor-performings such as intensity, acrylate has that low price, mechanical strength be high, ageing-resistant, yellowing-resistant, resistance to water
The advantage such as good, but there is the shortcomings such as organic solvent resistance is poor, poor heat resistance, softening point are relatively low, wear no resistance.Polyurethane
Having the biggest complementarity in performance with polyacrylate, if both being combined, the aqueous that can prepare excellent performance is gathered
Urethane acrylate coating, can also reduce the cost of synthesis simultaneously.
Acrylic ester modified water-soluble polyurethane resin commonly uses physical modification and two kinds of methods of chemical modification.Physical blending process is grasped
Make simple, easy to use, but the poor compatibility of two kinds of resins, and there is no chemical action between the two, it is easily generated separated, is blended
Resin stability is poor, transmitance is low, poor-performing；Chemical modification method is by acrylic resin and polyurethane resin by copolymerization
Structural bond pick up, the premium properties of the two can be given full play to, be better than physical blending process.
Summary of the invention
The present invention seeks to: provide a kind of utilize acrylic graft-modified method to promote its combination property (as resistance to always
Change, resistance to water etc.), the cost of reduction synthesis simultaneously, improves the system of the acrylic ester grafted modified aqueous polyurethane resin of cost performance
Preparation Method.
The technical scheme is that the preparation method of a kind of acrylic ester grafted modified aqueous polyurethane resin, including
Following steps:
Step 1): PEPA Novomer being added reaction vessel, after vacuum dehydration, is passed through nitrogen, temperature controls
80～90 DEG C, in stirring downhill reaction container, then drip diisocyanate, wherein diisocyanate and polyester polyols
The mol ratio of alcohol Novomer is 2～4:1, reacts 1～2 hour at 80～90 DEG C, obtain base polyurethane prepolymer for use as I after dropping；
Dripping diisocyanate in PEPA Novomer, main purpose is to allow PEPA Novomer keep
Amount, controls the molecular structure of product with this；
Step 2): by step 1) the base polyurethane prepolymer for use as I that obtains cools to less than 60 DEG C, by molten for dry multi-hydroxy carboxy acid
Solution in N-Methyl pyrrolidone after join in reaction vessel, then in reaction vessel drip glycol monomer, drip 0.5
～1 hour, after dropping, then it is warmed up to 70～80 DEG C, reacts 2.5～3.5 hours, course of reaction adds diluent, instead
The base polyurethane prepolymer for use as II containing hydrophilic group should be obtained after terminating；Multi-hydroxy carboxy acid be dissolved in N-Methyl pyrrolidone be in order to
Allow multi-hydroxy carboxy acid can participate in reaction more fully；The speed of dropping glycol monomer to be controlled well, to prevent dihydroxylic alcohols with different
The temperature that cyanate group reaction acutely causes rises sharply；
Step 3): step 2) the polyurethane prepolymer II that obtains cools to less than 60 DEG C, in reaction vessel, dropping is pre-
First it is dissolved with the acrylic monomers A of hydroquinone, drips 0.5～1 hour, after completion of dropwise addition, be warming up to 60～70 DEG C, react 2.5
～3.5 hours, then drip the acrylic monomers B being dissolved with azodiisobutyronitrile in advance, drip 1～1.5 hour, drip off rear 60
～70 DEG C be incubated 1～2 hour, obtain polyurethane acroleic acid oligomer；
Step 4): by step 3) the polyurethane acroleic acid oligomer that obtains cools to 50～60 DEG C, add under stirring
Enter in organic amine with become salt, organic amine and multi-hydroxy carboxy acid's mol ratio are 1～1.05:1, add deionized water, stirring 30～
60min, emulsifying is obtained the acrylic ester grafted modified aqueous polyurethane resin that solid content is 30～45%, is made by salt-forming reaction
Product can be dispersed in water uniformly, forms stable emulsion.
As preferred technical scheme, described diisocyanate selected from toluene di-isocyanate(TDI), 4,4-diphenyl methane two
Isocyanates, isophorone diisocyanate, hexamethylene diisocyanate, ring penta diisocyanate or hydrogenation of benzene methylmethane two
One in isocyanates.
As the mol ratio 1.0～1.1:1 of preferred technical scheme, described diisocyanate and hydroxyl total amount, wherein hydroxyl
Base is from PEPA Novomer, glycol monomer, multi-hydroxy carboxy acid, acrylic monomers A.
As preferred technical scheme, described multi-hydroxy carboxy acid is selected from dihydromethyl propionic acid or dimethylolpropionic acid, wherein
It is 2～7% that carboxyl in multi-hydroxy carboxy acid accounts for the mass percent of participation reaction monomers gross weight, and described reaction monomers includes that two is different
Cyanate, PEPA Novomer, multi-hydroxy carboxy acid, dihydroxylic alcohols, acrylic monomers A.
As preferred technical scheme, described glycol monomer is selected from BDO, 1,3 butylene glycol, a contracting diethyl two
Alcohol, propylene glycol, methyl propanediol, 1, the one in 6-hexanediol or neopentyl glycol.
As preferred technical scheme, described acrylic monomers A is selected from 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, methyl
One in 2-(Acryloyloxy)ethanol or Hydroxypropyl methacrylate.
As preferred technical scheme, described acrylic monomers B is butyl acrylate, methyl methacrylate, methyl-prop
In olefin(e) acid, acrylic acid, acrylic acid-2-ethyl caproite, isobornyl methacrylate and butyl methacrylate any three kinds
Mixture.
As preferred technical scheme, described organic amine is selected from triethylamine, N, in N-dimethylethanolamine or triethanolamine
One.
As preferred technical scheme, the molecular weight of described PEPA Novomer is 1000～2000, and its molecule is tied
Structure is as follows:
The invention have the advantage that the present invention to pass through strictly to control the proportioning of reaction mass, response time, charging sequence and anti-
Answer the selection of monomer, make the acrylic ester grafted modified aqueous polyurethane resin excellent combination property prepared (as ageing-resistant, water-fast
Property etc.), storage stability is good, stores half a year phase more than, and concrete advantage is as follows:
(1) by controlling the charging sequence of main material and charging process, (diisocyanate is instilled polyester polyols by the first step
The method of alcohol Novomer, second step introduces hydrophilic group carboxyl and chain extender diol monomer, and the 3rd step introduces double bond, then
Carry out double-bond polymerization reaction), obtain molecular structure and control preferably, the product of excellent combination property, and mature production technology is stable,
The covering with paint in plastics, woodenware and metal surface can be applied；
(2) by selecting PEPA Novomer to be used as polyurethane molecular main chain, the hardness obtaining product is high, power
Performance is good；
(3) by controlling carboxyl-content and carboxyl distribution on molecular backbone, the resin making synthesis can be uniform
It is dispersed in water, and can store for a long time；
(4) by controlling to add the amount of glycol monomer, in the case of other main material proportionings are constant, acrylic acid is regulated
The amount of monomer A, controls the introduction volume of double bond；
(5) ratio by adjusting each component of acrylic monomers B controls polyreaction, synthesizes different molecular structures
Acrylic ester grafted modified aqueous polyurethane resin, it is noted that rate of addition when being simultaneously added dropwise acrylic monomers B, otherwise polymerization is anti-
Should too fast if can produce implode, temperature to be controlled well；
(6) by directly causing polymerization in a solvent, compared to the aqueous first synthesizing end acrylic after introducing double bond
Then polyurethane polymeric monomer carries out the emulsion copolymerization of acrylic monomer, reduces the response time, improves polymerization efficiency；
(7) by controlling the proportioning of PEPA Novomer and diisocyanate, in Molecular regulator chain, soft chain segment is with hard
The proportioning of segment, while making the resin of synthesis meet high rigidity, takes into account again pliability；
(8) by the strict reaction temperature controlling each stage and time, synthesis technique is stable, and resin property is stable.
Final resin outward appearance is milky white colour band blue light emulsion；Solid content is about 40%；Become film hardness > 3H；Ageing-resistant, resistance to
Water is greatly improved；Storage stability is good, and 5～30 DEG C store the time more than half a year.
Acrylic ester grafted modified aqueous polyurethane resin prepared by the present invention has taken into account aqueous polyurethane and acrylic acid
Combination property, compensate for the deficiency in the Property of Waterborne Polyurethane of PEPA Novomer synthesis, the high (> 3H of hardness), attachment
Power 0 grade, resistance to water, ageing-resistant performance are good, improve the combination property of the aqueous polyurethane of PEPA Novomer synthesis,
Reduce cost simultaneously, improve its cost performance and competitiveness.
Detailed description of the invention
Embodiment 1
Prepare acrylic ester grafted modified aqueous polyurethane resin according to the following steps:
Outfit raw material:
Another it is equipped with appropriate deionized water, acetone (diluent), N-Methyl pyrrolidone；
PEPA Novomer molecular weight is about 1000, and carboxyl-content is about 5%, and 2-(Acryloyloxy)ethanol content is about
5.2%, hydroquinone content is about 0.001%, and acrylic monomer content is about 21%, and mol ratio is as follows: 2,4-toluene two
Isocyanates: PEPA Novomer: dihydromethyl propionic acid: methyl propanediol: 2-(Acryloyloxy)ethanol: triethylamine is about
3.8:1.0:1.0:0.6:1.2:1.0。
The resin outward appearance prepared is milky white colour band blue light emulsion, and solid content is about 36%, and stability of emulsion is good, hardness
> 3H, adhesive force 0 grade, water-fast, ageing-resistant.
Embodiment 2
Prepare acrylic ester grafted modified aqueous polyurethane resin according to the following steps:
Outfit raw material:
| Raw material | Consumption (g) |
| Isophorone diisocyanate | 33.6 |
| PEPA Novomer (molecular weight 1000) | 43.5 |
| Dihydromethyl propionic acid | 5.2 |
| Neopentyl glycol | 5.5 |
| Dibutyl tin laurate | 0.1 |
| Hydroxyethyl methylacrylate | 2.6 |
| Methyl methacrylate | 8.7 |
| Isobornyl methacrylate | 3.3 |
| Acrylic acid | 0.9 |
| Hydroquinone | 0.01 |
| Azodiisobutyronitrile | 0.1 |
| Triethanolamine | 4.5 |
Another it is equipped with appropriate deionized water, acetone (diluent), N-Methyl pyrrolidone；
PEPA Novomer molecular weight is about 1000, and carboxyl-content is about 4.2%, methylpropanoic acid hydroxyl ethyl ester content
Being about 2.5%, hydroquinone content is about 0.001%, and dibutyl tin laurate content is about 0.01%, and acrylic monomers contains
Amount is about 15%, and mol ratio is as follows: isophorone diisocyanate: PEPA Novomer: dihydromethyl propionic acid: new
Pentanediol: hydroxyethyl methylacrylate: triethanolamine is about 3.6:1.0:1.0:0.8:0.8:1.0.
The resin outward appearance prepared is milky white colour band blue light emulsion, and solid content is about 39%, and stability of emulsion is good, hardness
> 3H, adhesive force 0 grade, water-fast, ageing-resistant.
| Raw material | Consumption (g) |
| Isophorone diisocyanate | 35.2 |
| PEPA Novomer (molecular weight 2000) | 40.3 |
| Dihydromethyl propionic acid | 6.5 |
| 1,4-butanediol | 4.6 |
| Dibutyl tin laurate | 0.1 |
| Hydroxypropyl methacrylate | 2.6 |
| Methyl methacrylate | 9.9 |
| Acrylic acid-2-ethyl caproite | 3.9 |
| Methacrylic acid | 1.3 |
| Hydroquinone | 0.01 |
| Azodiisobutyronitrile | 0.1 |
| Triethylamine | 5 |
Embodiment 3
Prepare acrylic ester grafted modified aqueous polyurethane resin according to the following steps:
Outfit raw material:
Another it is equipped with appropriate deionized water, acetone (diluent), N-Methyl pyrrolidone；
PEPA Novomer molecular weight is about 2000, and carboxyl-content is about 6%, Hydroxypropyl methacrylate content
Being about 2.5%, hydroquinone content is about 0.001%, and dibutyl tin laurate content is about 0.01%, and acrylic monomers contains
Amount is about 17%, and mol ratio is as follows: isophorone diisocyanate: PEPA Novomer: dihydromethyl propionic acid: 1,
4-butanediol: Hydroxypropyl methacrylate: triethylamine is about 3.8:1.0:1.0:0.6:1.2:1.0.
The resin outward appearance prepared is milky white colour band blue light emulsion, and solid content is about 40%, and stability of emulsion is good, hardness
> 3H, adhesive force 0 grade, water-fast, ageing-resistant.
The principle of above-described embodiment only illustrative present invention and effect thereof, not for limiting the present invention.Any ripe
Above-described embodiment all can be modified under the spirit and the scope of the present invention or change by the personage knowing this technology.Cause
This, have usually intellectual such as complete with institute under technological thought without departing from disclosed spirit in art
All equivalences become are modified or change, and must be contained by the claim of the present invention.
Claims (9)
1. the preparation method of an acrylic ester grafted modified aqueous polyurethane resin, it is characterised in that comprise the following steps:
Step 1): PEPA Novomer is added reaction vessel, after vacuum dehydration, is passed through nitrogen, temperature control 80～
90 DEG C, in stirring downhill reaction container, then drip diisocyanate, wherein diisocyanate and PEPA
The mol ratio of Novomer is 2～4:1, reacts 1～2 hour at 80～90 DEG C, obtain base polyurethane prepolymer for use as I after dropping；
Step 2): by step 1) the base polyurethane prepolymer for use as I that obtains cools to less than 60 DEG C, dry multi-hydroxy carboxy acid is dissolved in
Join after in N-Methyl pyrrolidone in reaction vessel, in reaction vessel, then drip glycol monomer, drip 0.5～1
Hour, after dropping, then it is warmed up to 70～80 DEG C, reacts 2.5～3.5 hours, course of reaction adds diluent, reaction knot
The base polyurethane prepolymer for use as II containing hydrophilic group is obtained after bundle；
Step 3): step 2) the polyurethane prepolymer II that obtains cools to less than 60 DEG C, drips the most molten in reaction vessel
Solution has the acrylic monomers A of hydroquinone, drips 0.5～1 hour, is warming up to 60～70 DEG C after completion of dropwise addition, reaction 2.5～
3.5 hours, then drip the acrylic monomers B being dissolved with azodiisobutyronitrile in advance, drip 1～1.5 hour, drip off after 60～
70 DEG C are incubated 1～2 hour, obtain polyurethane acroleic acid oligomer；
Step 4): by step 3) the polyurethane acroleic acid oligomer that obtains cools to 50～60 DEG C, there was added under stirring
In machine amine with become salt, organic amine and multi-hydroxy carboxy acid's mol ratio are 1～1.05:1, add deionized water, stirring 30～
60min, emulsifying obtains the acrylic ester grafted modified aqueous polyurethane resin that solid content is 30～45%.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
Described diisocyanate selected from toluene di-isocyanate(TDI), 4,4-methyl diphenylene diisocyanate, isophorone diisocyanate,
One in hexamethylene diisocyanate, ring penta diisocyanate or hydrogenation of benzene dicyclohexylmethane diisocyanate.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
Described diisocyanate and the mol ratio 1.0～1.1:1 of hydroxyl total amount, wherein hydroxyl is from PEPA Novomer, binary
Alcohol monomer, multi-hydroxy carboxy acid, acrylic monomers A.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
Described multi-hydroxy carboxy acid is selected from dihydromethyl propionic acid or dimethylolpropionic acid, and wherein the carboxyl in multi-hydroxy carboxy acid accounts for participation reaction
The mass percent of total weight of monomer is 2～7%, and described reaction monomers includes diisocyanate, PEPA Novomer, many
Hydroxy carboxylic acid, dihydroxylic alcohols, acrylic monomers A.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
Described glycol monomer selected from BDO, 1,3 butylene glycol, diglycol, propylene glycol, methyl propanediol, 1,6-oneself
One in glycol or neopentyl glycol.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
Described acrylic monomers A is selected from 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxyethyl methylacrylate or methacrylic acid hydroxypropyl
One in ester.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
Described acrylic monomers B be butyl acrylate, methyl methacrylate, methacrylic acid, acrylic acid, acrylic acid-2-ethyl oneself
The mixture of any three kinds in ester, isobornyl methacrylate and butyl methacrylate.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
Described organic amine is selected from triethylamine, N, the one in N-dimethylethanolamine or triethanolamine.
The preparation method of acrylic ester grafted modified aqueous polyurethane resin the most according to claim 1, it is characterised in that
The molecular weight of described PEPA Novomer is 1000～2000, and its molecular structure is as follows:
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675467A (en) * | 2016-12-09 | 2017-05-17 | 尹先敏 | Preparation method of polyurethane foam adhesive for composite heat insulated board |
| CN109535335A (en) * | 2018-11-21 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of aqueous acrylic modified polyurethane resin and preparation method thereof |
| CN110028629A (en) * | 2019-04-28 | 2019-07-19 | 南京林业大学 | A kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves |
| CN112225849A (en) * | 2020-10-28 | 2021-01-15 | 石家庄市春羽科技有限公司 | Preparation method of acrylate modified polyurethane aqueous dispersion resin |
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| WO2006057796A2 (en) * | 2004-11-23 | 2006-06-01 | Bomar Specialties Co. | Coprolactone-grafted phenoxy resin oligomer and formulations containing it |
| WO2011063171A1 (en) * | 2009-11-23 | 2011-05-26 | Isp Investments Inc. | A reactive solution of polymerizable polymer comprising polymerizable reactive functionalities, process and compositions thereof |
| CN105461863A (en) * | 2015-12-23 | 2016-04-06 | 中山大学惠州研究院 | Acrylate modified waterborne polyurethane emulsion and preparation method thereof |
| CN105601861A (en) * | 2016-02-23 | 2016-05-25 | 同光（江苏）信息科技有限公司 | Synthetic method for organosilicone modified waterborne polyurethane resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006057796A2 (en) * | 2004-11-23 | 2006-06-01 | Bomar Specialties Co. | Coprolactone-grafted phenoxy resin oligomer and formulations containing it |
| WO2011063171A1 (en) * | 2009-11-23 | 2011-05-26 | Isp Investments Inc. | A reactive solution of polymerizable polymer comprising polymerizable reactive functionalities, process and compositions thereof |
| CN105461863A (en) * | 2015-12-23 | 2016-04-06 | 中山大学惠州研究院 | Acrylate modified waterborne polyurethane emulsion and preparation method thereof |
| CN105601861A (en) * | 2016-02-23 | 2016-05-25 | 同光（江苏）信息科技有限公司 | Synthetic method for organosilicone modified waterborne polyurethane resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675467A (en) * | 2016-12-09 | 2017-05-17 | 尹先敏 | Preparation method of polyurethane foam adhesive for composite heat insulated board |
| CN109535335A (en) * | 2018-11-21 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of aqueous acrylic modified polyurethane resin and preparation method thereof |
| CN110028629A (en) * | 2019-04-28 | 2019-07-19 | 南京林业大学 | A kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves |
| CN110028629B (en) * | 2019-04-28 | 2021-07-23 | 南京林业大学 | Preparation method of longifolene-based acrylate modified waterborne polyurethane |
| CN112225849A (en) * | 2020-10-28 | 2021-01-15 | 石家庄市春羽科技有限公司 | Preparation method of acrylate modified polyurethane aqueous dispersion resin |
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Application publication date: 20161116 |
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