WO2022117017A1 - 含有共聚物p的水性二次分散体及其制备方法和应用 - Google Patents
含有共聚物p的水性二次分散体及其制备方法和应用 Download PDFInfo
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- WO2022117017A1 WO2022117017A1 PCT/CN2021/134931 CN2021134931W WO2022117017A1 WO 2022117017 A1 WO2022117017 A1 WO 2022117017A1 CN 2021134931 W CN2021134931 W CN 2021134931W WO 2022117017 A1 WO2022117017 A1 WO 2022117017A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acrylate
- meth
- monomer
- parts
- hydroxyl
- Prior art date
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- 239000006185 dispersion Substances 0.000 title claims abstract description 62
- 229920001577 copolymer Polymers 0.000 title claims abstract description 44
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- 239000000178 monomer Substances 0.000 claims abstract description 187
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 140
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 62
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
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- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical group CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
Definitions
- water-based coatings are becoming a research hotspot in the current coatings industry due to their non-toxic, non-flammable, environmentally friendly, and energy-saving advantages.
- the waterborne two-component system of hydroxyacrylic acid (ester) dispersion and isocyanate curing agent is widely used in wood, metal, and other excellent properties due to its high gloss, good weather resistance, color retention and gloss retention. and other industrial paint applications. In some application scenarios, it can even be comparable to oily systems, and the development prospects are very broad.
- the bubble-free film thickness of the resin and the corresponding paint can be determined by spraying the sample with gradient film thickness. As the thickness of the paint film increases, the ability of gas to escape gradually weakens until pinholes and bubbles appear. The film thickness in this area is is the bubble-free film thickness of the system. On the premise of ensuring other properties, the higher the bubble-free film thickness of the system, the better.
- CN 101622309A discloses a method for increasing the thickness of resin-free bubble-free film. This patent improves the application of coatings by introducing a high boiling point non-polar solvent into the formulation. However, the introduced high-boiling point solvent usually cannot be completely evaporated under the conditions of baking, especially low-temperature curing, thereby greatly reducing the hardness and resistance of the paint film, which seriously restricts the practical applicability of this method.
- the second object of the present invention is to provide a method for preparing an aqueous secondary dispersion containing the copolymer P.
- the third object of the present invention is to provide a water-based paint.
- the present invention adopts the following technical solutions:
- aqueous secondary dispersion containing a copolymer P characterized in that the copolymer P is synthesized from the following components:
- Hydroxyl-containing hydrophobic polymers comprising the following components as structural unit monomers:
- Hydroxyl-containing hydrophilic polymers comprising the following components as structural unit monomers:
- the content of hydroxyl-containing hydrophobic polymer and hydroxyl-containing hydrophilic polymer is:
- copolymer P is synthesized from the following components:
- Hydroxyl-containing hydrophobic polymers comprising the following components as structural unit monomers:
- Hydroxyl-containing hydrophilic polymers comprising the following components as structural unit monomers:
- the solid fraction of the aqueous secondary dispersion is 30%-70%, preferably 40%-60%.
- the molecular weight of the copolymer P is 4000-10000 g/mol, preferably 5000-8000 g/mol.
- structural unit monomers of the hydroxyl-containing hydrophobic polymer and/or the hydroxyl-containing hydrophilic polymer also contain monomer Y;
- the monomer Y is an acrylate monomer prepared from a carboxyl group-containing monomer and tertiary glycidyl carbonate ring-opening, and the content of the monomer Y accounts for 2-10 wt% of the total content of each component of the copolymer P.
- R 1 and R 2 are each independently selected from alkyl groups, and the total number of carbon atoms of R 1 and R 2 is 7.
- A1 and A2 are each independently at least one selected from the group consisting of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.
- D carboxyl group-containing monomer is selected from at least one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid.
- the B1 acrylate monomer is selected from methyl (meth)acrylate, sec-butyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate Butyl, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, cocoate (meth)acrylate, octadecyl (meth)acrylate base ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycol di( Meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)
- the B1 vinyl monomer is selected from vinyl acetate, dichloroethylene, styrene, acrylonitrile, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methylol At least one of (meth)acrylamide and divinylbenzene.
- the B2 acrylate monomer and/or vinyl monomer are selected from one or more of methyl methacrylate, styrene, cyclic methacrylate, and isobornyl methacrylate.
- a preparation method of an aqueous secondary dispersion containing copolymer P comprising the steps:
- the structural unit monomers and initiators that form the hydroxyl-containing hydrophobic polymer are added to the solvent at the reaction temperature, and the first heat preservation;
- the present invention also provides an aqueous coating material, which comprises the aqueous secondary dispersion containing the copolymer P as described in the above-mentioned first object.
- the water-based paint also includes a crosslinking agent.
- crosslinking agent is selected from one or more of hydrophilic polyisocyanates and hydrophobic polyisocyanates.
- the aqueous secondary dispersion provided by the present invention is specially designed for the hydroxyl-containing hydrophilic polymer (dispersion shell polymer), so that its constituent monomers include high Tg acrylate monomers and/or vinyl monomers
- hydroxyl-containing hydrophilic polymer dispersion shell polymer
- its constituent monomers include high Tg acrylate monomers and/or vinyl monomers
- the hydrophilic polymer segment gradually thawed and started to move under baking, participating in the curing. Therefore, the hardness and resistance of the paint film will not be lost.
- the monomer Y is preferably added to increase the distance between the polymer segments, which can also help reduce the viscosity of the polymer and improve the thickness of the bubble-free film.
- the water-based paint coating film obtained by combining the water-based secondary dispersion and the water-based diisocyanate curing agent has the characteristics of excellent construction applicability, high gloss, high hardness and excellent weather resistance.
- the present invention provides an aqueous secondary dispersion containing the copolymer P, so that the aqueous secondary dispersion of the aqueous coating can improve the bubble-free film thickness of the aqueous coating while maintaining the It has good construction applicability, high gloss, hardness and good weather resistance.
- the prepared dispersion is very suitable for preparing a paint film with a high bubble-free film thickness and significantly improved construction and application performance.
- the aqueous secondary dispersion is an acrylic dispersion, wherein the copolymer P is synthesized from the following components:
- the copolymer P is synthesized from the following components:
- Hydroxyl-containing hydrophobic polymer in terms of the total mass of the structural unit monomers forming the hydroxyl-containing hydrophobic polymer, the hydroxyl-containing hydrophobic polymer contains the following components as structural unit monomers:
- Hydroxyl-containing hydrophilic polymer in terms of the total mass of the structural unit monomers forming the hydroxyl-containing hydrophilic polymer, the hydroxyl-containing hydrophilic polymer contains the following components as structural unit monomers:
- the foam-free film of the resin will be improved. Thickness is significantly improved, and at the same time, hardness and weather resistance (especially in low humidity, high temperature and low humidity environments) are good.
- the Tg of the homopolymer of the B2 acrylate monomer and/or vinyl monomer is greater than 80°C. Under this condition, the effect of improving the non-foam film thickness, hardness and weather resistance of the resin is better.
- B2 acrylate monomers and/or vinyl monomers are selected from one or more of methyl methacrylate, styrene, cyclic methacrylate, and isobornyl methacrylate.
- Hydroxyl-containing monomers suitable for A1 and A2 may include, but are not limited to, at least one selected from the group consisting of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate.
- the hydroxyl group-containing monomers in A1 and A2 may be the same or different.
- hydroxyethyl (meth)acrylate means hydroxyethyl methacrylate or hydroxyethyl acrylate.
- Other substances written in this way also have the same meaning, and will not be repeated here.
- the B1 acrylate monomer is selected from methyl (meth)acrylate, sec-butyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylic acid Isobutyl, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, cocoate (meth)acrylate, octadecyl (meth)acrylate Alkyl ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycol diethyl ether (Meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene
- the B1 vinylic monomer is selected from vinyl acetate, vinylidene chloride, styrene, acrylonitrile, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-methylol At least one of (meth)acrylamide and divinylbenzene.
- the D carboxyl group-containing monomer is selected from at least one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid.
- B2 acrylate monomer and/or vinyl monomer are selected from methyl methacrylate, styrene, cyclic methacrylate (for example, cyclohexyl methacrylate), methacrylic acid One or more of isobornyl esters.
- the structural unit monomer of the hydroxyl group-containing hydrophobic polymer and/or the hydroxyl group-containing hydrophilic polymer further contains monomer Y; wherein, the monomer Y is composed of a carboxyl group-containing monomer and a tertiary Acrylate monomer prepared by ring-opening of glycidyl carbonate.
- the introduction of the monomer Y can reduce the viscosity of the polymer, and at the same time, it can also help to improve the bubble-free film thickness of the coating containing the aqueous secondary dispersion.
- the basic properties of the paint film (particularly hardness and resistance) remain well maintained while the resin application applicability is significantly improved (improvement in film thickness without bubbles).
- a suitable monomer Y is an acrylate monomer prepared by ring-opening a carboxyl group-containing monomer and tertiary glycidyl carbonate, wherein the carboxyl group-containing monomers are preferably methacrylic acid and acrylic acid.
- the ring-opening reaction is carried out under the condition that a polymerization inhibitor is added between 100-150°C.
- the preparation method of monomer Y comprises the steps:
- R 1 and R 2 are each independently selected from alkyl groups, and the total number of carbon atoms of R 1 and R 2 is 7. Under this preferred condition, the obtained coating containing the aqueous secondary dispersion has a higher bubble-free film thickness, and has more obvious improvement effects such as hardness and weather resistance.
- the content of the monomer Y preferably accounts for 2-10 wt% of the total content of each component of the copolymer P.
- the content of the monomer Y includes, but is not limited to, 2-8 wt %, 4-10 wt %, 4-8 wt %, etc. of the total content of each component of the copolymer P.
- the content of the hydroxyl group-containing hydrophobic polymer and the hydroxyl group-containing hydrophilic polymer is:
- Hydroxyl-containing hydrophobic polymer 50-90wt%
- a suitable molecular weight of the copolymer P is 4000-10000 g/mol, preferably 5000-8000 g/mol.
- the structural unit monomers that is, components A1 and B1
- initiators that form hydroxyl-containing hydrophobic polymers are added to the solvent at the reaction temperature, and the first heat preservation is performed at the polymerization temperature;
- each incubation time is independently 0.5-2 hours.
- reaction temperature is determined by the chosen initiation system.
- the temperature after cooling is preferably 80-120°C.
- the polymerization method of the unsaturated monomer is well known to those skilled in the art.
- the reaction solvent is placed in the reaction kettle, and the monomer and the initiator are added dropwise to carry out the polymerization.
- the initiator is selected from azobisisobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, tert-butyl peroxyacetate, tert-amyl peroxyacetate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-tert-valerate , at least one of di-tert-butyl peroxide and di-tert-amyl peroxide.
- the amount of initiator used is determined according to the desired molecular weight.
- the solvent is selected from butyl acetate, diethylene glycol dimethyl ether, solvent oil No. 100, solvent oil No. 200, toluene, xylene, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone isobutyl ketone, cyclohexanone, isophorone, diacetone alcohol, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, ethylene glycol ethyl ether acetate Ester, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate,
- the solvent or solvent mixture is selected according to the principle that the boiling point of the solvent is slightly higher than the reaction temperature.
- the solvent content is determined by the solid content of the copolymer P at the end of the polymerization being between 50% and 90%, particularly preferably between 70% and 85%.
- the neutralizing agent is preferably an organic amine neutralizing agent.
- Organic amines are used to neutralize the carboxyl groups on the P segment of the copolymer to provide sufficient water-based ability of the resin.
- the organic amine is selected from ammonia, triethylamine, triethanolamine, dimethylethanolamine, 2-methyl-2-aminopropanol, dimethylisopropanolamine, methyldiethanolamine, ethyldiethanolamine At least one of isopropylamine and diethylethanolamine; the degree of neutralization is 50-110%, preferably 75-100%.
- Yet another embodiment of the present invention provides an aqueous coating material comprising the aqueous secondary dispersion containing the copolymer P as described above.
- the water-based paint can be prepared by contacting and mixing the water-based dispersion resin with a cross-linking agent.
- the crosslinking agent is selected from one or more of hydrophilic polyisocyanates and hydrophobic polyisocyanates.
- monomer Y is prepared by the above-mentioned preparation method.
- Embodiment 1 (hard monomer is styrene, the content in P2 is 50wt%)
- Embodiment 2 (hard monomer is cyclohexyl methacrylate, the content in P2 is 50wt%)
- hydroxyethyl acrylate 70 parts of butyl methacrylate, 50 parts of butyl acrylate, 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, kept for 1 hour, then cooled to a certain temperature and added 25 parts of triethyl After the amine is kept for 0.5 hours, 1000 parts of deionized water is finally added dropwise, and the material is filtered and discharged after the temperature is kept for 1 hour to obtain an aqueous secondary dispersion of hydroxy acrylate.
- hydroxyethyl acrylate 50 parts of styrene, 70 parts of butyl acrylate, 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, keep warm for 1 hour, then cool down to a certain temperature and add 25 parts of triethylamine and keep warm After 0.5 hours, 1000 parts of deionized water was finally added dropwise, and the material was filtered and discharged after being kept for 1 hour to obtain an aqueous secondary dispersion of hydroxyacrylate.
- the bubble-free film thickness was tested under the conditions of 35°C and 40%RH. It was used with Covestro 3900 curing agent. With the help of automatic spraying equipment, the gradient film thickness was sprayed on the tinplate plate. The baking condition was 60°C*1h. Bubble boundaries and test.
- Comparative Example 1 since its hydrophobic polymer does not contain hard monomers, its bubble-free film thickness is relatively low, which affects the construction applicability.
- Comparative Example 2 although some hard monomers (styrene) were introduced into the hydrophobic polymer segment, the content thereof was relatively low, and although the thickness of the bubble-free film was improved, it was not obvious.
- Comparative Example 6 the bubble-free film thickness of the resin was improved by introducing a long carbon chain acrylate structure into the resin structure, but the introduction of the monomer greatly weakened the glass transition temperature, resulting in a softer paint film and affecting the final performance.
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)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种含有共聚物P的水性二次分散体,所述共聚物P由以下组分合成:1)包含以下组分作为结构单元单体的含羟基疏水聚合物:A1含羟基单体,B1丙烯酸酯单体和/或乙烯类单体,以及2)包含以下组分作为结构单元单体的含羟基亲水聚合物:A2含羟基单体,B2均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体,C均聚物的Tg在80℃以下的丙烯酸酯单体,D含羧基单体。该分散体的无泡膜厚较高的同时其他诸如硬度,耐性均未有明显损失;同时耐候性好,可耐受低湿、尤其是高温低湿的施工环境。本发明还公开了该分散体的制备方法和应用。
Description
本发明涉及涂料技术领域。更具体地,涉及一种含有共聚物P的水性二次分散体及其制备方法和应用。
近年来,随着国家环保政策的日趋严厉,水性涂料由于其无毒、不燃、环境友好、节省能源等优点,正成为当前涂料行业的研究热点。在这些水性涂料中,羟基丙烯酸(酯)分散体和异氰酸酯固化剂搭配的水性双组分体系,因具有光泽高、耐候性好、保色保光等一些优异性能而被广泛应用于木器、金属等工业漆应用领域。在某些应用场景下甚至可以媲美油性体系,发展前景非常广阔。
但在实际的应用中,环境的湿度比较低的时候,尤其是在高温低湿的施工环境中,当漆膜厚度达到一定水平,板面经常会出现一些气泡或者针孔,严重影响到漆膜的外观和性能。这是因为在漆膜厚涂的时候,混在涂料中的因搅拌带入的气体和异氰酸酯基团与水反应生成的二氧化碳等气体不能全部溢出而产生的缺陷。其中,气泡是气体在穿透漆膜表面时遭遇漆膜固化而留下的外观缺陷。遇到这样的情况,我们通常将该涂料体系描述为施工应用性较差,严重影响外观,无法在客户现场使用。采取喷涂梯度膜厚的样板的方式可以确定树脂以及相应涂料的无泡膜厚,随着漆膜的厚度增加,气体溢出的能力逐步减弱,直至出现针孔和气泡,该区域处的膜厚即为体系的无泡膜厚。在确保其他各项性能的前提下,体系的无泡膜厚越高越好。
目前,有一些相关的专利报道来提高树脂的无泡膜厚进而确保相应涂料的施工应用性。CN 101622309A公开了一种提升树脂无泡膜厚的方法。该专利通过向配方中引入高沸点非极性溶剂的方式提升涂料的施工应用性。但引入的高沸点溶剂通常无法在烘烤尤其是低温固化的条件下蒸发完全,进而大幅降低漆膜的硬度和耐性,这严重制约该方法的实际应用性。
有鉴于此,有必要提供一种施工应用性优异的羟基丙烯酸酯水分散体,该分散体的无泡膜厚较高的同时其他诸如硬度,耐性均未有明显损失,以解决现有技术存在的问题。
发明内容
本发明的第一个目的在于提供一种含有共聚物P的水性二次分散体,该分散体的无泡膜厚较高的同时其他诸如硬度,耐性均未有明显损失;同时耐候性好,可耐受低湿、尤其是高温低湿的施工环境。
本发明的第二个目的在于提供一种含有共聚物P的水性二次分散体的制备方法。
本发明的第三个目的在于提供一种水性涂料。
为达到上述目的,本发明采用下述技术方案:
一种含有共聚物P的水性二次分散体,其特征在于,所述共聚物P由以下组分合成:
1)包含以下组分作为结构单元单体的含羟基疏水聚合物:
A1含羟基单体,
B1丙烯酸酯单体和/或乙烯类单体,以及
2)包含以下组分作为结构单元单体的含羟基亲水聚合物:
A2含羟基单体,
B2均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体,
C均聚物的Tg在80℃以下的丙烯酸酯单体,
D含羧基单体。
进一步地,所述共聚物P中,含羟基疏水聚合物与含羟基亲水聚合物的含量为:
含羟基疏水聚合物 50-90wt%;
含羟基亲水聚合物 10-50wt%。
进一步地,所述共聚物P由以下组分合成:
1)包含以下组分作为结构单元单体的含羟基疏水聚合物:
A1含羟基单体 10-30wt%,
B1丙烯酸酯单体和/或乙烯类单体 70-90wt%,以及
2)包含以下组分作为结构单元单体的含羟基亲水聚合物:
A2含羟基单体 15-35wt%,
B2均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体 40-70wt%,
C均聚物的Tg在80℃以下的丙烯酸酯单体 0-10wt%,
D含羧基单体 10-15wt%。
进一步地,所述水性二次分散体的固体分为30%-70%,优选为40%-60%。
进一步地,所述共聚物P的分子量为4000-10000g/mol,优选为5000-8000g/mol。
进一步地,含羟基疏水聚合物和/或含羟基亲水聚合物的结构单元单体中还含有单体Y;
其中,单体Y为由含羧基单体和叔碳酸缩水甘油酯开环制备得到的丙烯酸酯单体,且单体Y的含量占共聚物P各组分总含量的2-10wt%。
进一步地,所述单体Y的结构式如下式I所示:
其中,R
1和R
2各自独立的选自烷基,且R
1与R
2的总碳原子数为7。
进一步地,A1和A2含羟基单体各自独立地选自(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯中的至少一种。
进一步地,D含羧基单体选自丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸中的至少一种。
进一步地,B1丙烯酸酯单体选自(甲基)丙烯酸甲酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸椰子油酸酯、(甲基) 丙烯酸十八烷基酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二乙氨基乙酯、(甲基)丙烯酸二甲氨基丙酯、(甲基)丙烯酸缩水甘油酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯中的至少一种。
进一步地,B1乙烯类单体选自醋酸乙烯、二氯代乙烯、苯乙烯、丙烯腈、(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、二乙烯基苯中的至少一种。
进一步地,B2丙烯酸酯单体和/或乙烯类单体选自甲基丙烯酸甲酯、苯乙烯、甲基丙烯酸环酯、甲基丙烯酸异冰片酯中的一种或几种。
为达到上述第二个目的,本发明采用下述技术方案:
一种含有共聚物P的水性二次分散体的制备方法,包括如下步骤:
在氮气气氛下,于反应温度下向溶剂中加入形成含羟基疏水聚合物的结构单元单体和引发剂,第一次保温;
加入形成含羟基亲水聚合物的结构单元单体和引发剂,进行第二次保温;
降温,加入中和剂,进行第三次保温;
加入去离子水进行乳化,进行第四次保温;
过滤,得所述含有共聚物P的水性二次分散体。
为达到上述第三个目的,本发明还提供一种水性涂料,该水性涂料中包含如上第一个目的所述的含有共聚物P的水性二次分散体。
进一步地,所述水性涂料中还包含交联剂。
进一步地,所述交联剂选自亲水性聚异氰酸酯、疏水性聚异氰酸酯中的一种或几种。
本发明的有益效果如下:
本发明提供的水性二次分散体由于对含羟基亲水聚合物(分散体壳层聚合物)进行了特殊设计,使得其组成单体中包含高Tg的丙烯酸酯单体和/或乙烯类单体,将其用于水性涂料的制备中时,在早期与固化剂交联时,由于链段运动减弱,反应速度有所降低使得涂层在溶剂挥发过程中的粘度下降,进而给气泡的释放创造条件,最终使得树脂的无泡膜厚得到明显的改善,明显改善树脂施工应用性。且随着固化的进行,亲水聚合物链段在烘烤下逐步解冻开始运动,参与固化。所以并不会损失漆膜的硬度和各项耐性。进一步地,本发明提供的水性二次分散体中,优选加入的单体Y使得聚合链段间的距离拉大,也可以帮助降低聚合物的粘度,改善无泡膜厚。
本发明提供的水性涂料中,由该水性二次分散体与水性二异氰酸酯固化剂配合得到的水性涂料涂膜具有施工应用性优异,光泽高、硬度高、耐候性优良的特点。
为了更清楚地说明本发明,下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
根据本发明的一个具体实施方式,本发明中提供一种含有共聚物P的水性二次分散体,以使得水性涂料用水性二次分散体在改善水性涂料的无泡膜厚厚度的同时,保持其 具有好的施工应用性,高的光泽、硬度和好的耐候性。
本发明中发现,通过对该水性二次分散体的共聚物中聚合物链段独特设计,制备得到的分散体非常适合制备高无泡膜厚、且施工应用性能得到明显改善的漆膜。本发明中,该水性二次分散体为丙烯酸分散体,其中,所述共聚物P由以下组分合成:
1)包含以下组分作为结构单元单体的含羟基疏水聚合物(P1):
A1含羟基单体,
B1丙烯酸酯单体和/或乙烯类单体,以及
2)包含以下组分作为结构单元单体的含羟基亲水聚合物(P2):
A2含羟基单体,
B2均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体,
C均聚物的Tg在80℃以下的丙烯酸酯单体,
D含羧基单体。
在一个优选示例中,所述共聚物P由以下组分合成:
1)含羟基疏水聚合物,以形成该含羟基疏水聚合物的结构单元单体的总的质量计,该含羟基疏水聚合物中包含以下组分作为结构单元单体:
A1含羟基单体 10-30wt%,
B1丙烯酸酯单体和/或乙烯类单体 70-90wt%,以及
2)含羟基亲水聚合物,以形成该含羟基亲水聚合物的结构单元单体的总的质量计,该含羟基亲水聚合物中包含以下组分作为结构单元单体:
A2含羟基单体 15-35wt%,
B2均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体 40-70wt%,
C均聚物的Tg在80℃以下的丙烯酸酯单体 0-10wt%,
D含羧基单体 10-15wt%。
通常而言,丙烯酸分散体存在至少两段聚合物,一段为亲水聚合物,一段为疏水聚合物,中和乳化后,亲水聚合物充当乳化剂将疏水聚合物包裹在内分散于水中。常规的设计都是选择内硬外软的方式来进行聚合物的设计。目前几乎没有针对亲水聚合物也就是分散体壳层聚合物的玻璃化温度展开研究。我们意外地发现,当含羟基亲水聚合物的组成单体中包含有上述特定量的均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体时,树脂的无泡膜厚得到明显的改善,同时,硬度、耐候性(尤其是低湿、高温低湿等环境)好。
在一个优选示例中,所述B2丙烯酸酯单体和/或乙烯类单体的均聚物的Tg>80℃。在此条件下,对树脂的无泡膜厚的提高、硬度及耐候性的改善效果更好。
示例性的,B2丙烯酸酯单体和/或乙烯类单体选自甲基丙烯酸甲酯、苯乙烯、甲基丙烯酸环酯、甲基丙烯酸异冰片酯中的一种或几种。
适合于A1和A2中的含羟基单体可包括但不限于选自(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯中的至少一种。且,A1和A2中含羟基单体可相同也可不相同。
需要说明的是,本发明中,(甲基)丙烯酸羟乙酯是指甲基丙烯酸羟乙酯或丙烯酸羟乙酯。其他的这种写法的物质也是同样类似的意思,在此不赘述。
示例性的,B1丙烯酸酯单体选自(甲基)丙烯酸甲酯、(甲基)丙烯酸仲丁酯、(甲 基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸椰子油酸酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二乙氨基乙酯、(甲基)丙烯酸二甲氨基丙酯、(甲基)丙烯酸缩水甘油酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯中的至少一种。
示例性的,B1乙烯类单体选自醋酸乙烯、二氯代乙烯、苯乙烯、丙烯腈、(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、二乙烯基苯中的至少一种。
在一个优选示例中,D含羧基单体选自丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸中的至少一种。
在一个优选示例中,B2丙烯酸酯单体和/或乙烯类单体选自甲基丙烯酸甲酯、苯乙烯、甲基丙烯酸环酯(例如,可为甲基丙烯酸环己酯)、甲基丙烯酸异冰片酯中的一种或几种。
示例性的,C丙烯酸酯单体选自丙烯酸甲酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸椰子油酸酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二乙氨基乙酯、(甲基)丙烯酸二甲氨基丙酯、(甲基)丙烯酸缩水甘油酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯中的至少一种。
在一个优选示例中,本实施方式中,含羟基疏水聚合物和/或含羟基亲水聚合物的结构单元单体中还含有单体Y;其中,单体Y为由含羧基单体和叔碳酸缩水甘油酯开环制备得到的丙烯酸酯单体。本发明中发现,单体Y的引入可以使得聚合物的粘度降低,同时还可有助于改善提高包含该水性二次分散体的涂料的无泡膜厚。在明显改善树脂施工应用性(无泡膜厚改善)的同时,漆膜的基础性能(特别是硬度和耐性)保持良好。
适合的单体Y为由含羧基单体和叔碳酸缩水甘油酯开环制备得到的丙烯酸酯单体,其中,含羧基单体优选甲基丙烯酸和丙烯酸。优选地,开环反应在100-150℃之间添加阻聚剂的条件下进行。
进一步地,单体Y的制备方法包括如下步骤:
200-300份的叔碳酸缩水甘油酯和60-80份的丙烯酸以及0-1份的对羟基苯甲醚混合后加入到反应釜并加热到100-160℃,之后测试酸价,直至酸价小于1mgKOH/g,降温至室温出料。
单体Y的结构式优选如下式I所示:
其中,R
1和R
2各自独立的选自烷基,且R
1与R
2的总碳原子数为7。在此优选条件下, 得到的包含该水性二次分散体的涂料的无泡膜厚更高、硬度、耐候性等改善效果更明显。
单体Y的含量优选占共聚物P各组分总含量的2-10wt%。示例性的,单体Y的含量包括但不限于为占共聚物P各组分总含量的2-8wt%、4-10wt%、4-8wt%等。
在一个优选示例中,所述共聚物P中,含羟基疏水聚合物与含羟基亲水聚合物的含量为:
含羟基疏水聚合物 50-90wt%;
含羟基亲水聚合物 10-50wt%。
本实施方式中,合适的共聚物P的分子量为4000-10000g/mol,优选为5000-8000g/mol。
本实施方式中,合适的该水性二次分散体的固体分为30-70%,优选为40-60%。
本发明的又一个具体实施方式提供了如上所述的含有共聚物P的水性二次分散体的制备方法,包括如下步骤:
在氮气气氛下,于反应温度下向溶剂中加入形成含羟基疏水聚合物的结构单元单体(也即组分A1和B1)和引发剂,在聚合温度下第一次保温;
加入形成含羟基亲水聚合物的结构单元单体(也即组分A2、B2、C和D)和引发剂,在聚合温度下进行第二次保温;
降温,加入中和剂,在中和温度范围内进行第三次保温;
加入去离子水进行乳化,50℃左右进行第四次保温;
过滤,得所述含有共聚物P的水性二次分散体。
示例性的,各保温时间各自独立地为0.5-2小时。
此外,上述反应温度由所选引发体系决定。降温后的温度优选为80-120℃。
本实施方式中,不饱和单体的聚合方法是本领域技术人员所熟知的,典型的是将反应溶剂置于反应釜内,开始滴加单体和引发剂进行聚合。
优选地,所述引发剂选自偶氮二异丁腈、过氧化二苯甲酰、过氧化二月桂酰、过氧化二异丙苯、过氧化醋酸叔丁酯、过氧化醋酸叔戊酯、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化-2-乙基己酸叔丁酯、过氧化-2-乙基己酸叔戊酯、过氧化叔戊酸叔丁酯、二叔丁基过氧化物、二叔戊基过氧化物中的至少一种。引发剂的使用量根据所期望的分子量来确定。
优选地,所述溶剂选自醋酸丁酯、二乙二醇二甲醚、100号溶剂油、200号溶剂油、甲苯、二甲苯、乙醇、异丙醇、正丁醇、丙酮、甲乙酮、甲基异丁基酮、环己酮、异佛尔酮、二丙酮醇、乙二醇乙醚、乙二醇丁醚、丙二醇甲醚、丙二醇乙醚、丙二醇丙醚、丙二醇丁醚、乙二醇乙醚醋酸酯、乙二醇丁醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯、二乙二醇甲醚、二乙二醇丁醚、二丙二醇甲醚、二丙二醇乙醚、二丙二醇丁醚、二丙二醇二甲醚中的至少一种。根据溶剂沸点略高于反应温度的原则来选择溶剂或溶剂的混合物。溶剂含量通过共聚物P聚合结束时的固体分在50%-90%之间来确定,尤其优选70%-85%之间。
本实施方式中,中和剂优选为有机胺中和剂。采用有机胺中和共聚物P链段上的羧基以提供树脂足够的水性化能力。优选地,所述有机胺选自氨水、三乙胺、三乙醇胺、二甲基乙醇胺、2-甲基-2-氨基丙醇、二甲基异丙醇胺、甲基二乙醇胺、乙基二异丙胺、二乙基 乙醇胺中的至少一种;中和度为50-110%,优选为75-100%。
采用去离子水乳化得到最终的羟基丙烯酸酯水分散体,以达到最终分散体所需的固体分。
本发明的又一个实施方式提供包含如上所述的含有共聚物P的水性二次分散体的水性涂料。
具体地,将所述水性分散体树脂与交联剂接触进行混合,即可制得所述水性涂料。优选地,所述交联剂选自亲水性聚异氰酸酯、疏水性聚异氰酸酯中的一种或几种。
以下结合一些具体实施例对本发明的技术方案进行说明:
单体Y的制备
单体Y的制备方法包括如下步骤:
200-300份的叔碳酸缩水甘油酯和60-80份的丙烯酸以及0-1份的对羟基苯甲醚混合后加入到反应釜并加热到100-160℃,之后测试酸价,直至酸价小于1mgKOH/g,降温至室温出料。,,得单体Y,其结构式如下式I所示:
以下各实施例中,如无特殊说明,单体Y均是通过上述制备方法制备得到的。
实施例1(硬单体为苯乙烯,在P2中的含量为50wt%)
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、120份甲基丙烯酸正丁酯、80份单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、120份苯乙烯、20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
实施例2(硬单体为甲基丙烯酸环己酯,在P2中的含量为50wt%)
加入200份二丙二醇甲醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、120份甲基丙烯酸丁酯、80份单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、120份甲基丙烯酸环己酯、20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
实施例3
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、120份甲基丙烯酸丁酯、80份单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、120份甲基丙烯酸环己酯、20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
实施例4
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括140份丙烯酸正丁酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、220份甲基丙烯酸丁酯、40份单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括40份甲基丙烯酸羟乙酯、120份苯乙烯、20份丙烯酸、40份单体Y)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
实施例5
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括140份丙烯酸正丁酯、220份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、40份自制单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括40份甲基丙烯酸羟乙酯、120份甲基丙烯酸异冰片酯、20份丙烯酸、40份自制单体Y)和1.5份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
实施例6
加入200份二丙二醇甲醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、120份甲基丙烯酸丁酯、80份自制单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、120份甲基丙烯酸甲酯、20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
实施例7
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括140份丙烯酸正丁酯、220份甲基丙烯酸甲酯、140份丙烯酸异辛酯、140份苯乙 烯、160份甲基丙烯酸羟乙酯)和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括40份甲基丙烯酸羟乙酯、120份甲基丙烯酸异冰片酯、20份丙烯酸、40份自制单体Y)和1.5份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
比较例1
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、200份甲基丙烯酸丁酯)和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、70份甲基丙烯酸丁酯、50份丙烯酸丁酯,20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到羟基丙烯酸酯水性二次分散体。
比较例2
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、200份甲基丙烯酸丁酯)和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、50份苯乙烯、70份丙烯酸丁酯,20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到羟基丙烯酸酯水性二次分散体。
比较例3
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、200份甲基丙烯酸异冰片酯)和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、50份苯乙烯、70份丙烯酸丁酯,20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到羟基丙烯酸酯水性二次分散体。
比较例4
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、120份甲基丙烯酸正丁酯、80份单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、70份苯乙烯、50份丙烯酸正丁酯,20份丙烯酸)和2份二叔戊基过氧化物后,保温1小 时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
比较例5
加入200份丙二醇丁醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、120份甲基丙烯酸正丁酯、80份单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括50份甲基丙烯酸羟乙酯、145份苯乙烯、5份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
比较例6
加入200份二丙二醇甲醚,在氮气的保护下加热升温至150℃,滴加第一部分单体混合物(包括100份丙烯酸正丁酯、100份甲基丙烯酸甲酯、100份丙烯酸异辛酯、140份苯乙烯、160份甲基丙烯酸羟乙酯、120份甲基丙烯酸丁酯、80份单体Y))和5份二叔戊基过氧化物,保温1小时,继续滴加第二部分单体混合物(包括60份甲基丙烯酸羟乙酯、120份丙烯酸月桂酯、20份丙烯酸)和2份二叔戊基过氧化物后,保温1小时,然后降温至一定温度加入25份三乙胺后保温0.5小时,最后滴加1000份去离子水,保温1小时后过滤出料,得到所述无泡膜厚优良的羟基丙烯酸酯水性二次分散体。
各实施例与对比例的性能测试结果如下表1所示:
表1
注:
无泡膜厚在35℃、40%RH条件下测试,搭配科思创3900固化剂使用,借助自动化喷涂设备,在马口铁板上喷涂梯度膜厚,烘烤条件为60℃*1h,之后观察起泡界限并测试。
纵观比较例1的单体组成和配方,由于其疏水聚合物不含有硬单体,其无泡膜厚较低,影响施工应用性。而比较例2尽管在疏水聚合物段引入了部分硬单体(苯乙烯),但其含量较低,在无泡膜厚层面虽有提升,但并不明显。而比较例6通过向树脂结构中引入长碳链丙烯酸酯结构的方式提升了树脂的无泡膜厚,但由于该单体的引入大幅削弱玻璃化温度,导致漆膜偏软,影响最终性能。
本发明所制备的羟基丙烯酸酯水分散体,其合成过程简单可操作、树脂无泡膜厚高、硬度耐性均满足应用要求,可作为双组分聚氨酯涂料的C羟基树脂组分,和水性、油性二异氰酸酯组分配制高性能水性聚氨酯涂料。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (10)
- 一种含有共聚物P的水性二次分散体,其特征在于,所述共聚物P由以下组分合成:1)包含以下组分作为结构单元单体的含羟基疏水聚合物:A1含羟基单体,B1丙烯酸酯单体和/或乙烯类单体,以及2)包含以下组分作为结构单元单体的含羟基亲水聚合物:A2含羟基单体,B2均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体,C均聚物的Tg在80℃以下的丙烯酸酯单体,D含羧基单体。
- 根据权利要求1所述的含有共聚物P的水性二次分散体,其特征在于,所述共聚物P由以下组分合成:1)包含以下组分作为结构单元单体的含羟基疏水聚合物:A1含羟基单体 10-30wt%,B1丙烯酸酯单体和/或乙烯类单体 70-90wt%,以及2)包含以下组分作为结构单元单体的含羟基亲水聚合物:A2含羟基单体 15-35wt%,B2均聚物的Tg大于80℃的丙烯酸酯单体和/或乙烯类单体 40-70wt%,C均聚物的Tg在80℃以下的丙烯酸酯单体 0-10wt%,D含羧基单体 10-15wt%。
- 根据权利要求1所述的含有共聚物P的水性二次分散体,其特征在于,所述共聚物P中,含羟基疏水聚合物与含羟基亲水聚合物的含量为:含羟基疏水聚合物 50-90wt%;含羟基亲水聚合物 10-50wt%。
- 根据权利要求1所述的含有共聚物P的水性二次分散体,其特征在于,所述水性二次分散体的固体分为30%-70%,优选为40%-60%。
- 根据权利要求1所述的含有共聚物P的水性二次分散体,其特征在于,所述共聚物P的分子量为4000-10000g/mol,优选为5000-8000g/mol。
- 根据权利要求1-5任一项所述的含有共聚物P的水性二次分散体,其特征在于,含羟基疏水聚合物和/或含羟基亲水聚合物的结构单元单体中还含有单体Y;其中,单体Y为由含羧基单体和叔碳酸缩水甘油酯开环制备得到的丙烯酸酯单体,且单体Y的含量占共聚物P各组分总含量的2-10wt%。
- 根据权利要求1所述的含有共聚物P的水性二次分散体,其特征在于,A1和A2含羟基单体各自独立地选自(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟丁酯中的至少一种;优选地,D含羧基单体选自丙烯酸、甲基丙烯酸、衣康酸、富马酸、马来酸中的至少一种;优选地,B1丙烯酸酯单体选自(甲基)丙烯酸甲酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸椰子油酸酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二乙氨基乙酯、(甲基)丙烯酸二甲氨基丙酯、(甲基)丙烯酸缩水甘油酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯中的至少一种;优选地,B1乙烯类单体选自醋酸乙烯、二氯代乙烯、苯乙烯、丙烯腈、(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、二乙烯基苯中的至少一种;优选地,B2丙烯酸酯单体和/或乙烯类单体选自甲基丙烯酸甲酯、苯乙烯、甲基丙烯酸环酯、甲基丙烯酸异冰片酯中的一种或几种;优选的,C丙烯酸酯单体选自丙烯酸甲酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸椰子油酸酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸二乙氨基乙酯、(甲基)丙烯酸二甲氨基丙酯、(甲基)丙烯酸缩水甘油酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯中的至少一种。
- 如权利要求1-8任一项所述的含有共聚物P的水性二次分散体的制备方法,其特征在于,包括如下步骤:在氮气气氛下,于反应温度下向溶剂中加入形成含羟基疏水聚合物的结构单元单体和引发剂,第一次保温;加入形成含羟基亲水聚合物的结构单元单体和引发剂,进行第二次保温;降温,加入中和剂,进行第三次保温;加入去离子水进行乳化,进行第四次保温;过滤,得所述含有共聚物P的水性二次分散体。
- 包含如权利要求1-8任一项所述的含有共聚物P的水性二次分散体的水性涂料。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115612434A (zh) * | 2022-10-19 | 2023-01-17 | 厦门三德信科技股份有限公司 | 一种耐低温丙烯酸酯压敏胶及其制备方法 |
CN115677915A (zh) * | 2022-11-14 | 2023-02-03 | 湖南湘江关西涂料(长沙)有限公司 | 丙烯酸树脂及其制备方法、涂料及涂膜制品 |
CN115894785A (zh) * | 2022-12-21 | 2023-04-04 | 广东碳和新材料科技有限公司 | 一种生物基羟基丙烯酸树脂水分散体及其制备方法和应用 |
CN117186750A (zh) * | 2023-09-11 | 2023-12-08 | 雅图高新材料股份有限公司 | 一种水性真空镀铝罩光清漆及其制备方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101914185A (zh) * | 2010-09-08 | 2010-12-15 | 廊坊金汇利工业涂料有限公司 | 一种羟基丙烯酸树脂水分散体及用其制备的水性涂料 |
CN102850703A (zh) * | 2011-06-27 | 2013-01-02 | 上海涂料有限公司技术中心 | 一种含羟基聚丙烯酸酯二级水分散体的制备方法 |
CN106117419A (zh) * | 2016-07-26 | 2016-11-16 | 立邦涂料(中国)有限公司 | 一种含羟基的丙烯酸水分散体及其制备方法 |
CN106543381A (zh) * | 2016-12-02 | 2017-03-29 | 立邦涂料(中国)有限公司 | 一种含羟基聚丙烯酸酯水分散体及其制备方法 |
CN108264643A (zh) * | 2017-12-19 | 2018-07-10 | 万华化学(宁波)有限公司 | 一种共聚物p、水性分散体树脂及其在水性涂料中的应用 |
US20190112404A1 (en) * | 2016-03-18 | 2019-04-18 | Sun Chemical Corporation | Polar functional non-aqueous acrylic dispersions |
-
2020
- 2020-12-02 CN CN202011386527.4A patent/CN114573743A/zh active Pending
-
2021
- 2021-12-02 WO PCT/CN2021/134931 patent/WO2022117017A1/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101914185A (zh) * | 2010-09-08 | 2010-12-15 | 廊坊金汇利工业涂料有限公司 | 一种羟基丙烯酸树脂水分散体及用其制备的水性涂料 |
CN102850703A (zh) * | 2011-06-27 | 2013-01-02 | 上海涂料有限公司技术中心 | 一种含羟基聚丙烯酸酯二级水分散体的制备方法 |
US20190112404A1 (en) * | 2016-03-18 | 2019-04-18 | Sun Chemical Corporation | Polar functional non-aqueous acrylic dispersions |
CN106117419A (zh) * | 2016-07-26 | 2016-11-16 | 立邦涂料(中国)有限公司 | 一种含羟基的丙烯酸水分散体及其制备方法 |
CN106543381A (zh) * | 2016-12-02 | 2017-03-29 | 立邦涂料(中国)有限公司 | 一种含羟基聚丙烯酸酯水分散体及其制备方法 |
CN108264643A (zh) * | 2017-12-19 | 2018-07-10 | 万华化学(宁波)有限公司 | 一种共聚物p、水性分散体树脂及其在水性涂料中的应用 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115612434A (zh) * | 2022-10-19 | 2023-01-17 | 厦门三德信科技股份有限公司 | 一种耐低温丙烯酸酯压敏胶及其制备方法 |
CN115677915A (zh) * | 2022-11-14 | 2023-02-03 | 湖南湘江关西涂料(长沙)有限公司 | 丙烯酸树脂及其制备方法、涂料及涂膜制品 |
CN115677915B (zh) * | 2022-11-14 | 2023-11-10 | 湖南湘江关西涂料(长沙)有限公司 | 丙烯酸树脂及其制备方法、涂料及涂膜制品 |
CN115894785A (zh) * | 2022-12-21 | 2023-04-04 | 广东碳和新材料科技有限公司 | 一种生物基羟基丙烯酸树脂水分散体及其制备方法和应用 |
CN117186750A (zh) * | 2023-09-11 | 2023-12-08 | 雅图高新材料股份有限公司 | 一种水性真空镀铝罩光清漆及其制备方法 |
CN117186750B (zh) * | 2023-09-11 | 2024-03-15 | 雅图高新材料股份有限公司 | 一种水性真空镀铝罩光清漆及其制备方法 |
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