CN113088153B - Chlorinated polypropylene/acrylate hybrid aqueous dispersion as well as preparation method and application thereof - Google Patents
Chlorinated polypropylene/acrylate hybrid aqueous dispersion as well as preparation method and application thereof Download PDFInfo
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- CN113088153B CN113088153B CN201911334242.3A CN201911334242A CN113088153B CN 113088153 B CN113088153 B CN 113088153B CN 201911334242 A CN201911334242 A CN 201911334242A CN 113088153 B CN113088153 B CN 113088153B
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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
- C09D151/003—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 by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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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
- 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
Abstract
The invention relates to a chlorinated polypropylene/acrylate hybrid aqueous dispersion, a preparation method and application thereof, the preparation method can realize good compatibility between chlorinated polypropylene and acrylic resin, the obtained aqueous dispersion has good storage stability, and the aqueous dispersion has excellent adhesion performance and excellent water resistance on PP and other base materials, can be used for a PP base material primer to realize good adhesion between a PP base material and a finish paint, and can also be matched with a water-based isocyanate curing agent to obtain the finish paint with excellent adhesion performance of the PP base material.
Description
Technical Field
The invention relates to the field of acrylate emulsion, and in particular relates to a chlorinated polypropylene/acrylate hybrid aqueous dispersion, and a preparation method and application thereof.
Technical Field
The polypropylene material has excellent performances of light weight, good toughness, no toxicity, no smell, low price and the like, and also has good molding processability, and is widely applied to the fields of automobiles, electronics, toys and the like. However, due to the characteristics of polypropylene materials, such as non-polar materials, high crystallinity, low surface energy, and the like, the surface of the polypropylene materials is difficult to wet and adhere. At present, PP water (a solvent-type chlorinated polypropylene solution with the content of about 20 percent) is generally adopted to enhance the adhesion capability of the surface of the polypropylene material and simultaneously improve the compatibility with other resins. However, the large amount of organic solvent causes VOC emission and causes serious environmental pollution.
In recent years, with the increasing awareness of environmental protection and the strict national restrictions on volatile organic compounds in coating systems, chlorinated polypropylene resins are made water-based, and the solution of chlorinated polypropylene solution in solvent form is being replaced to enhance the surface adhesion of nonpolar materials such as polypropylene, which is the development direction in the field. For example, the preparation method of the aqueous chlorinated polypropylene emulsion disclosed in the Chinese invention patent CN109280134A, and the chlorinated polypropylene modified acrylic resin with excellent boiling resistance and the preparation method thereof disclosed in the Chinese invention patent CN109293839 all carry out hydration on the chlorinated polypropylene, reduce VOC and solve the problem of adhesion of nonpolar base materials such as polypropylene and the like. However, the chlorinated polypropylene material structure and the acrylic resin structure are different, so that the compatibility of the chlorinated polypropylene material structure and the acrylic resin structure is relatively poor, and the obtained water-based emulsion has the problems of poor stability and poor water resistance.
Disclosure of Invention
The invention provides a chlorinated polypropylene/acrylate hybrid aqueous dispersion prepared from the following reaction raw materials
The preparation method comprises the following steps:
(A) modified acrylate polymer: from 15% by weight to 50% by weight, preferably from 25 to 40% by weight,
(B) chlorinated polypropylene: from 2% by weight to 15% by weight, preferably from 2 to 10% by weight,
(C) water: from 40% by weight to 68% by weight, preferably from 55% by weight to 65% by weight,
(D) catalyst: 0.05 to 1.1 wt.%, preferably 0.1 to 1.0 wt.%,
(E) initiator: 0.15% to 1.5%, preferably 0.3% to 1.3%,
based on the mass of the chlorinated polypropylene/acrylate hybrid aqueous dispersion.
Further, the modified acrylate polymer is prepared by the reaction of the following reaction components
(A1) A non-functional (meth) acrylic monomer or a derivative thereof: 20 to 78 wt.%, preferably 30 to 60 wt.%,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: 0 to 25 wt.%, preferably 0 to 10 wt.%,
(A3) a carboxyl-functional (meth) acrylic monomer or derivative thereof: 2.0% to 10% by weight, preferably 3% to 5% by weight,
(A4) other radically polymerizable monomers: from 10% by weight to 55% by weight, preferably from 15% by weight to 40% by weight,
based on the total mass of the components.
In the present invention, the modified acrylate polymer further comprises hydroxyl-terminated polybutadiene as component (A5), and the amount thereof added is 0.5 to 6.0% by weight, preferably 0.5 to 3% by weight, for example, 0.6, 1, 2% by weight, based on the total mass of components (A1) to (A5).
In the present invention, the hydroxyl group content of the hydroxyl-terminated polybutadiene of component (A5) is 0.5% -0.8%, and the number average molecular weight is 2000-4500.
In the invention, the catalyst is organic amine, preferably one or more of N, N-dimethylethanolamine, triethanolamine and N, N-diethylethanolamine,
in the present invention, the non-functional (meth) acrylic monomer or derivative thereof of component (a1) includes one or more of methyl (meth) acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isobornyl (meth) acrylate, and norbornyl (meth) acrylate.
The non-functional (meth) acrylic monomer or derivative thereof of the component (A1) contains at least one hydrocarbon-based (meth) acrylate of C12-C25 in an amount of 15wt% to 55wt%, preferably 20wt% to 40wt%, based on the total mass of the component (A1).
The alkyl (meth) acrylate of C12-C25 is preferably dodecyl (meth) acrylate, tridecyl (meth) acrylate;
component (A2) the hydroxy-functional (meth) acrylic monomer or derivative thereof comprises one or more mixtures of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate;
the carboxyl functional (meth) acrylic monomer or its derivative of component (a3) includes one or more of a radically polymerizable monomer with a sulfonic acid group, a radically polymerizable monomer with a carboxylic acid group, a radically polymerizable monomer with a phosphate salt, a radically polymerizable monomer with a sulfonate salt, a monoalkyl ester of a divalent acid, and a monoalkyl ester of a divalent acid anhydride, and is more preferably selected from the radically polymerizable monomers with a carboxylic acid group; the free-radically polymerizable monomer with a carboxylic acid group is preferably selected from acrylic acid and/or methacrylic acid; preferably, the carboxyl functional (meth) acrylic monomer or derivative thereof comprises one or more of (meth) acrylic acid, crotonic acid, maleic acid, 3- (cyclohexane) -1-propanesulfonic acid, sodium sulfamate;
the other radical polymerizable monomer of component (a4) includes one or more of styrene, (meth) acrylonitrile, acrylamide.
In the present invention, the chlorine content of the chlorinated polypropylene is 15wt% to 45wt%, preferably 19wt% to 33 wt%.
In the present invention, the initiator is a peroxide radical initiator, such as one or more of di-tert-butyl peroxide, di-tert-amyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxypivalate and tert-butyl peroxyisopropylcarbonate,
in the invention, a neutralizing agent can be added into the dispersion, the neutralizing agent comprises one or more of ammonia water, sodium hydroxide, triethanolamine and N, N-dimethylethanolamine, and the adding amount of the neutralizing agent can be adjusted according to the required pH value.
According to the invention, an organic solvent can be added into the modified acrylate polymer according to the requirement, wherein the organic solvent comprises one or more of propylene glycol butyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, solvent oil, propylene glycol methyl ether, dipropylene glycol dimethyl ether, butyl acetate, toluene and xylene; the amount of the organic solvent to be added may be selected by those skilled in the art according to the reaction need, and may be, for example, 10wt% to 50wt% based on the total amount of the modified acrylate polymer.
The invention also provides a preparation method of the chlorinated polypropylene/acrylate hybrid aqueous dispersion, which comprises the following steps:
(1) polymerizing the following raw materials by radical polymerization to form a copolymer (W1):
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: from 30% by weight to 80% by weight, preferably from 40% by weight to 70%,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: from 0% by weight to 30% by weight, preferably from 0 to 20%,
(A4) other radically polymerizable monomers: 15% to 60% by weight, preferably 30% to 50% by weight,
(A5) hydroxyl-terminated polybutadiene: 0 or 0.6% to 10% by weight, preferably 1% to 5% by weight,
based on the total mass of the four component monomers added in the step (1),
(2) then, the following raw materials were further added to the copolymer (W1) and polymerized to synthesize a copolymer (W2):
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: 0 to 80 wt.%, preferably 20 to 80 wt.%,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: from 0 to 45% by weight, preferably from 0 to 35% by weight,
(A3) a carboxyl-functional (meth) acrylic monomer or a derivative thereof: from 5% by weight to 25% by weight, preferably from 12% by weight to 20% by weight,
(A4) other radically polymerizable monomers: from 0% by weight to 60% by weight, preferably from 0% by weight to 50% by weight,
the wt% is based on the total mass of the above four component monomers added in the step (2),
(3) adding chlorinated polypropylene polymer, adding catalyst after the chlorinated polypropylene polymer is completely softened and dissolved, further reacting, optionally neutralizing by a neutralizer, and adding water for dispersing to obtain the chlorinated polypropylene modified acrylate aqueous dispersion.
In the present invention, the ratio of the total mass of the monomers added when synthesizing the copolymer (W1) to the total mass of the monomers added in step (2) when synthesizing the copolymer (W2) is 0.2 to 4: 1, preferably 0.5-3.5: 1.
In the present invention, the polymerization temperature in the polymerization for synthesizing the copolymer (W1) is 80 to 160 ℃, preferably 120-150 ℃.
In the present invention, the polymerization temperature in the polymerization for synthesizing the copolymer (W2) is 80 to 160 ℃, preferably 120 ℃ to 150 ℃.
In the invention, in the polymerization reaction of synthesizing the copolymer (W1), each component monomer is added in a dropping mode, the dropping time is 2.0-5.0 hours, and the temperature is kept for 0.2-2.0 hours after the dropping is finished.
In the invention, in the step (2), each component monomer is added in a dropwise manner, the dropwise addition time is 0.5-2.0 hours, and the temperature is kept for 0.5-2.0 hours after the dropwise addition is finished.
In the present invention, the reaction temperature in the step (3) is 50 to 100 ℃, preferably 60 to 90 ℃, and the reaction time is 0.5 to 1.0 hour.
In the present invention, it is also necessary to add an initiator in the polymerization reaction of the synthetic copolymer (W1) and the polymerization reaction of the synthetic copolymer (W2), and in the polymerization reaction of the synthetic copolymer (W1), respectively, the amount of the initiator added is 0.5% to 4.0%, preferably 0.8% to 2.0%, based on the total mass of the components (A1) to (A5) added in step (1). In the polymerization reaction for synthesizing the copolymer (W2), the amount of the initiator to be added is 0.5 to 4.0%, preferably 0.8 to 2.0% based on the total mass of the components (A1) to (A5) added in step (2).
In the invention, when the copolymer (W1) is formed by polymerization, an organic solvent can be added, and the organic solvent comprises one or more of propylene glycol butyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, solvent oil, propylene glycol methyl ether, dipropylene glycol dimethyl ether, butyl acetate, toluene and xylene.
The invention also provides the application of the chlorinated polypropylene/acrylate hybrid aqueous dispersion in the aspect of water-based paint.
The invention has the beneficial effects that: the compatibility between the acrylate polymer and chlorinated polypropylene is increased by introducing the long-chain (methyl) acrylate monomer of C12-C25 alkyl, meanwhile, hydroxyl-terminated polybutadiene is further introduced into the acrylate part, the compatibility between the acrylate part and chlorinated polypropylene is further increased, in addition, a certain cross-linking structure can be introduced into a molecular weight chain by adding the hydroxyl-terminated polybutadiene, and the water resistance is obviously improved. The aqueous dispersion has good adhesive force and excellent water resistance on nonpolar base materials such as polypropylene and the like, and simultaneously has good miscibility with other aqueous resins. In addition, the aqueous dispersion obtained in the invention can also be used together with an isocyanate curing agent, so that the two-component finish paint with high adhesion performance on nonpolar base materials such as polypropylene and the like is improved.
The chlorinated polypropylene/acrylate dispersoid obtained by the invention has excellent stability, has good adhesive force on polyolefin base materials such as PP and the like, can be used as a PP polyolefin base material primer and an adhesive force promoter of the PP polyolefin base material, and has good compatibility with acrylate and polyurethane coatings; in addition, the dispersion product obtained by the invention has excellent water resistance when used as a primer.
Detailed Description
Embodiments of the present invention are illustrated in detail by the following examples, but the present invention is not limited to the following examples.
In the embodiment, the adhesion test is performed by adopting a PP (polypropylene) base material and a hundred-grid adhesion test method; the emulsion stability test adopts room temperature placement, and particle size change and whether demixing and sedimentation are carried out are observed; the test of water resistance of a paint film at 40 ℃ adopts a composite coating, the primer adopts the dispersion product in the invention, and the finish adopts two-component PUD;
description of raw materials:
BG: butyl cellosolve, dow chemical; source of raw materials
PNB: propylene glycol butyl ether, dow chemical;
DMEA: n, N-dimethylethanolamine, shanghai alatin biochemistry technologies ltd;
DTBP: di-tert-butyl peroxide, Lanzhou auxiliaries;
BPO: benzoyl peroxide, Lanzhou adjuvant plant;
CPP: chlorinated polypropylene: b3030 (chlorine content 19%), B2020 (chlorine content 26-28%), B1010 (chlorine content 33-37%), Nippon paper-making Co., Ltd;
hydroxyl-terminated polybutadiene: type III (hydroxyl value: 0.54-0.64, number average molecular weight: 3000-.
Example 1:
adding 80g BG into a 1L reactor containing a heating device, a condensing device and a stirring device, heating to 140 ℃, and starting to uniformly dropwise add the following monomer mixture when the initial material is heated to 140 ℃: 13.5g of isobutyl methacrylate, 70g of methylhydroxyethyl methacrylate, 60g of lauryl methacrylate, 174g of styrene, 40g of isooctyl acrylate, 2.5g of hydroxyl-terminated polybutadiene (type III), 10g of BG and 8g of DTBP, were added dropwise over a period of about 3 hours, and after the addition of the monomer mixture had ended, the mixture was kept at this temperature for 0.5 hour. The following monomer mixture was then added dropwise uniformly: 30g of hydroxypropyl acrylate, 50g of styrene, 12g of acrylic acid and 2g of DTBP, the dropping time is about 1 hour, the temperature is kept for 0.5 hour after the monomer mixture is dropped, then the reaction temperature is reduced to 90 ℃, chlorinated polypropylene B303050 g is added and stirred for 0.5 hour, then 5g N, N-dimethylethanolamine is added and continuously stirred for reaction for 0.5 hour, finally 5g of N, N-dimethylethanolamine is continuously added and stirred for 20 minutes, and 600g of water is dispersed for 0.5 hour to obtain the polypropylene/acrylate aqueous dispersion.
Example 2:
adding 80g BG into a 1L reactor containing a heating device, a condensing device and a stirring device, heating to 140 ℃, and starting to uniformly dropwise add the following monomer mixture when the initial material is heated to 140 ℃: 113g of isobutyl methacrylate, 45g of octadecyl methacrylate, 46g of styrene, 40g of isooctyl acrylate, 20g of hydroxyl-terminated polybutadiene (type IV), 10g of BG and 8g of DTBP, the dropping time being about 3 hours, and the temperature being maintained at this temperature for 0.5 hour after the completion of the dropping of the monomer mixture. The following monomer mixture was then added dropwise uniformly: 50g of methyl methacrylate, 30g of butyl acrylate, 20g of acrylic acid and 2g of DTBP, the dropping time is about 1 hour, the temperature is kept for 0.5 hour after the monomer mixture is dropped, then 80g of chlorinated polypropylene (B2020) is added and stirred for 0.5 hour after the reaction temperature is reduced to 90 ℃, then 5g N and N-dimethylethanolamine are added and stirred for reaction for 0.5 hour, finally 10g of N, N-dimethylethanolamine are added and stirred for 20 minutes, and 900g of water is dispersed for 0.5 hour to obtain the polypropylene/acrylate hybrid.
Example 3:
adding 160g BG into a 1L reactor containing a heating device, a condensing device and a stirring device, heating to 140 ℃, and starting to uniformly dropwise add the following monomer mixture when the temperature of an initial material is raised to 140 ℃: 50g of isobutyl methacrylate, 40g of dodecyl methacrylate, 50g of styrene, 2.5g of hydroxyl-terminated polybutadiene (III), 10g of BG and 5g of DTBP, the dropping time being about 3 hours, and the temperature being maintained at this temperature for 0.5 hour after the completion of the dropping of the monomer mixture. The following monomer mixture was then added dropwise uniformly: 35g of methyl methacrylate, 28g of butyl acrylate, 18g of acrylic acid and 2g of DTBP, the dropping time is about 1 hour, the temperature is kept for 0.5 hour after the monomer mixture is dropped, then 200g of chlorinated polypropylene (B1010) is added and stirred for 0.5 hour after the reaction temperature is reduced to 90 ℃, then 5g N and N-dimethylethanolamine are added and stirred for reaction for 0.5 hour, finally 10g of N, N-dimethylethanolamine are added and stirred for 20 minutes, and 880g of water is dispersed for 0.5 hour to obtain the polypropylene/acrylate aqueous dispersion hybrid.
Example 4:
adding 110g of PNB into a 1L reactor containing a heating device, a condensing device and a stirring device, heating to 140 ℃, and starting to uniformly dropwise add the following monomer mixture when the initial material is heated to 140 ℃: 20g of methyl methacrylate, 10g of isobutyl methacrylate, 60g of dodecyl methacrylate, 80g of styrene, 2g of hydroxyl-terminated polybutadiene (III), 10g of BG and 4g of DTBP, the dropping time being about 3 hours, and the temperature being maintained at this temperature for 0.5 hour after the completion of the dropping of the monomer mixture. The following monomer mixture was then added dropwise uniformly: 20g of methyl methacrylate, 20g of butyl acrylate, 40g of styrene, 10g of acrylic acid and 2g of DTBP, the dripping time is about 1 hour, the temperature is kept for 0.5 hour at the temperature after the monomer mixture is dripped, 28g of chlorinated polypropylene (B2020) is added and stirred for 0.5 hour after the reaction temperature is reduced to 90 ℃, 5g N and N-dimethylethanolamine are added and stirred for reaction for 0.5 hour, 10g of N, N-dimethylethanolamine is added and stirred for 20 minutes, and 900g of water is dispersed for 0.5 hour to obtain the polypropylene/acrylate hybrid aqueous dispersion.
Example 5:
adding 140g BG into a 1L reactor containing a heating device, a condensing device and a stirring device, heating to 90 ℃, and starting to uniformly dropwise add the following monomers for mixing when the initial material is heated to 90 ℃: 20g of dodecyl methacrylate, 30g of styrene, 2.5g of hydroxyl-terminated polybutadiene (III), 10g of BG and 2g of BPO are added dropwise over a period of about 1.0 hour, and the temperature is maintained at this temperature for 0.5 hour after the addition of the monomer mixture is completed. The following monomer mixture was then added dropwise uniformly: 35g of methyl methacrylate, 38g of butyl acrylate, 50g of hydroxyethyl methacrylate, 60g of styrene, 10g of acrylic acid and 5g of BPO, the dropping time is about 3.0 hours, after the monomer mixture is dropped, the temperature is kept for 0.5 hour at the temperature, 28g of chlorinated polypropylene (B2020) is added and stirred for 0.5 hour, then 3g N and N-dimethylethanolamine are added and stirred for reaction for 0.5 hour, finally 5g of N, N-dimethylethanolamine are added and stirred for 20 minutes, and 900g of water is dispersed for 0.5 hour to obtain the polypropylene/acrylate aqueous dispersion.
Comparative example 1:
adding 80g of BG into a 1L reactor containing a heating device, a condensing device and a stirring device, heating to 140 ℃, and uniformly dropwise adding the following monomer mixtures when the temperature of an initial material is raised to 140 ℃: 60g of methyl methacrylate, 80g of isobutyl methacrylate, 90g of styrene, 20g of isooctyl acrylate, 10g of BG and 4g of DTBP were added dropwise over a period of about 3 hours, and the temperature was maintained at this temperature for 0.5 hour after the addition of the monomer mixture. The following monomer mixture was then added dropwise uniformly: 30g of methyl methacrylate, 30g of butyl acrylate, 20g of styrene, 18g of acrylic acid and 1g of DTBP, the dropping time is about 1 hour, the temperature is kept for 0.5 hour at the temperature after the monomer mixture is dropped, then chlorinated polypropylene B202080 g is added and stirred for 0.5 hour after the reaction temperature is reduced to 90 ℃, then 5g N and N-dimethylethanolamine are added and stirred for 0.5 hour, finally 10g of N, N-dimethylethanolamine are added and stirred for 20 minutes, and 900g of water is dispersed for 0.5 hour to obtain the polypropylene/acrylate hybrid aqueous dispersion.
Comparative example 2:
adding 80g BG into a 1L reactor containing a heating device, a condensing device and a stirring device, heating to 140 ℃, and starting to uniformly dropwise add the following monomer mixture when the initial material is heated to 140 ℃: 60g of methyl methacrylate, 80g of isobutyl methacrylate, 60g of lauryl methacrylate, 90g of styrene, 20g of isooctyl acrylate, 10g of BG and 4g of DTBP, the dropping time is about 3 hours, and the temperature is kept for 0.5 hour after the monomer mixture is dropped. The following monomer mixture was then added dropwise uniformly: 30g of methyl methacrylate, 30g of butyl acrylate, 20g of styrene, 18g of acrylic acid and 1g of DTBP, the dropping time is about 1 hour, the temperature is kept for 0.5 hour at the temperature after the monomer mixture is dropped, then chlorinated polypropylene B202080 g is added and stirred for 0.5 hour after the reaction temperature is reduced to 90 ℃, then 5g N and N-dimethylethanolamine are added and stirred for 0.5 hour, finally 10g of N, N-dimethylethanolamine are added and stirred for 20 minutes, and 900g of water is dispersed for 0.5 hour to obtain the polypropylene/acrylate hybrid aqueous dispersion.
Examples comparison of properties:
Claims (28)
1. a chlorinated polypropylene/acrylate hybrid aqueous dispersion, characterized in that,
prepared by the reaction of the following reaction raw materials:
(A) modified acrylate polymer: 15 to 50 weight percent of the total weight of the mixture,
(B) chlorinated polypropylene: 2 to 15 weight percent of the total weight of the mixture,
(C) water: 40 to 68 weight percent of the total weight of the composition,
(D) catalyst: 0.05 wt% -1.1wt%,
(E) initiator: 0.15wt% -1.5 wt%,
based on the mass of the chlorinated polypropylene/acrylate hybrid aqueous dispersion;
the modified acrylate polymer is prepared by the reaction of the following reaction components:
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: 20 to 78 wt% of a catalyst,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: 0 to 25wt% of a catalyst,
(A3) a carboxyl-functional (meth) acrylic monomer or a derivative thereof: 2.0wt% -10wt%,
(A4) other radically polymerizable monomers: 10wt% to 55wt%,
based on the total mass of the components;
the modified acrylate polymer also comprises hydroxyl-terminated polybutadiene serving as a component (A5), and the adding amount of the hydroxyl-terminated polybutadiene is 0.5-6.0 wt% of the total mass of the components (A1) - (A5);
the preparation method of the chlorinated polypropylene/acrylate hybrid aqueous dispersion comprises the following steps:
(1) polymerizing the following raw materials by radical polymerization to form a copolymer (W1):
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: 30 to 80 weight percent of the total weight of the mixture,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: 0 to 30 weight percent of the total weight of the composition,
(A4) other radically polymerizable monomers: 15 to 60 weight percent of the total weight of the mixture,
(A5) hydroxyl-terminated polybutadiene: 0.6wt% to 10wt%,
based on the total mass of the four component monomers added in the step (1),
(2) then, the following raw materials were further added to the copolymer (W1) and polymerized to synthesize a copolymer (W2):
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: 0 to 80wt% of a catalyst,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: 0 to 45wt% of a catalyst,
(A3) a carboxyl-functional (meth) acrylic monomer or a derivative thereof: 5 to 25 weight percent of the total weight of the mixture,
(A4) other radically polymerizable monomers: 0wt% to 60wt%,
the wt% is based on the total mass of the above four component monomers added in the step (2),
(3) adding chlorinated polypropylene polymer, adding a catalyst after the chlorinated polypropylene polymer is completely softened and dissolved, further reacting, and finally, optionally neutralizing by a neutralizer, adding water for dispersing to obtain chlorinated polypropylene modified acrylate aqueous dispersion;
the component (A1) non-functional (methyl) acrylic monomer or derivative thereof at least contains one C12-C25 alkyl (methyl) acrylate, and the content of the alkyl (methyl) acrylate is 15-55 wt% of the total mass of the component (A1).
2. The dispersion of claim 1, prepared by a reaction comprising the following reaction starting materials:
(A) modified acrylate polymer: 25 to 40 weight percent of the total weight of the alloy,
(B) chlorinated polypropylene: 2 to 10 weight percent of a catalyst,
(C) water: 55 to 65 weight percent of the total weight of the mixture,
(D) catalyst: 0.1wt% -1.0wt%,
(E) initiator: 0.3wt% -1.3wt%,
based on the mass of the chlorinated polypropylene/acrylate hybrid aqueous dispersion.
3. The dispersion of claim 1, wherein the modified acrylate polymer is produced from a reaction comprising the following reaction components:
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: 30 to 60 weight percent of the total weight of the mixture,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: 0 to 10wt% of a catalyst,
(A3) a carboxyl-functional (meth) acrylic monomer or derivative thereof: 3 to 5 weight percent of the total weight of the mixture,
(A4) other radically polymerizable monomers: 15wt% -40wt%,
based on the total mass of the components;
the modified acrylate polymer also comprises hydroxyl-terminated polybutadiene serving as the component (A5), and the adding amount of the hydroxyl-terminated polybutadiene is 0.5-3 wt% of the total mass of the components (A1) - (A5).
4. The dispersion according to claim 1, characterized in that the process for the preparation of the chlorinated polypropylene/acrylate hybrid aqueous dispersion comprises the following steps:
(1) polymerizing the following raw materials by radical polymerization to form a copolymer (W1):
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: 40 to 70 percent of the total weight of the mixture,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: 0 to 20 percent of the total weight of the mixture,
(A4) other radically polymerizable monomers: 30 to 50 weight percent of the total weight of the mixture,
(A5) hydroxyl-terminated polybutadiene: 1 to 5 weight percent of the total weight of the composition,
based on the total mass of the four component monomers added in the step (1),
(2) then, the following raw materials were further added to the copolymer (W1) and polymerized to synthesize a copolymer (W2):
(A1) a non-functional (meth) acrylic monomer or a derivative thereof: 20 to 80 weight percent of the total weight of the mixture,
(A2) a hydroxy-functional (meth) acrylic monomer or derivative thereof: 0 to 35wt% of a catalyst,
(A3) a carboxyl-functional (meth) acrylic monomer or a derivative thereof: 12 to 20 weight percent of the total weight of the mixture,
(A4) other radically polymerizable monomers: 0wt% to 50wt%,
the wt% is based on the total mass of the above four component monomers added in the step (2),
(3) adding chlorinated polypropylene polymer, adding catalyst after the chlorinated polypropylene polymer is completely softened and dissolved, further reacting, and finally, optionally neutralizing by a neutralizer, adding water for dispersing to obtain the chlorinated polypropylene modified acrylate aqueous dispersion.
5. The dispersion as claimed in claim 1, wherein the hydroxyl-terminated polybutadiene of component (A5) has a hydroxyl group content of 0.5% to 0.8% and a number average molecular weight of 2000-4500.
6. The dispersion of claim 1, wherein the catalyst is an organic amine.
7. The dispersion of claim 6, wherein the catalyst is one or more of N, N-dimethylethanolamine, triethanolamine, N-diethylethanolamine.
8. The dispersion of claim 1, wherein component (a1) non-functional (meth) acrylic monomer or derivative thereof comprises one or more of methyl (meth) acrylate, butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate.
9. The dispersion of claim 1, wherein said non-functional (meth) acrylic monomer or derivative of component (a1) comprises at least one hydrocarbon-based (meth) acrylate of C12-C25 in an amount of 20wt% to 40wt% based on the total mass of component (a 1).
10. The dispersion of claim 1, wherein the C12-C25 hydrocarbon-based (meth) acrylate is dodecyl (meth) acrylate, tridecyl (meth) acrylate.
11. The dispersion of claim 1, wherein component (a2) hydroxy-functional (meth) acrylic monomer or derivative thereof comprises one or more of 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate, and 6-hydroxyhexyl acrylate.
12. The dispersion of claim 1, wherein component (a3) the carboxyl-functional (meth) acrylic monomer or derivative thereof comprises one or more of a free-radically polymerizable monomer with a sulfonic acid group, a free-radically polymerizable monomer with a carboxylic acid group, a free-radically polymerizable monomer with a phosphate group, a free-radically polymerizable monomer with a sulfonate group, a mono-alkyl ester of a divalent acid, and a mono-alkyl ester of a divalent acid anhydride.
13. A dispersion according to claim 12, characterised in that component (a3) the carboxy-functional (meth) acrylic monomer or derivative thereof is selected from free-radically polymerisable monomers with a carboxylic acid group; the free radical polymerizable monomer with a carboxylic acid group is selected from acrylic acid and/or methacrylic acid.
14. A dispersion according to claim 13, wherein the carboxy functional (meth) acrylic monomer or derivative thereof comprises one or more of (meth) acrylic acid, crotonic acid, maleic acid, 3- (cyclohexane) -1-propanesulfonic acid, sodium sulfamate.
15. The dispersion of claim 1, wherein component (a4) other free-radically polymerizable monomers include one or more of styrene, (meth) acrylonitrile, acrylamide.
16. The dispersion of claim 1, wherein the initiator is a peroxide-based free radical initiator comprising one or more of di-t-butyl peroxide, di-t-amyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxypivalate, and t-butyl peroxyisopropylcarbonate.
17. The dispersion of claim 1 wherein the modified acrylate polymer is further added with an organic solvent comprising one or more of propylene glycol butyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol butyl ether, mineral spirits, propylene glycol methyl ether, dipropylene glycol dimethyl ether, butyl acetate, toluene, xylene.
18. The dispersion of claim 1, wherein a neutralizing agent is added to the dispersion, wherein the neutralizing agent comprises one or more of ammonia, sodium hydroxide, triethanolamine, and N, N-dimethylethanolamine.
19. Dispersion according to claim 1, wherein chlorinated polypropylene having a chlorine content of 15% to 45% by weight is used.
20. A dispersion according to claim 19, characterised in that chlorinated polypropylene with a chlorine content of 19% to 33% by weight is used.
21. The dispersion according to claim 1, wherein the ratio of the total mass of monomers added during the synthesis of the copolymer (W1) to the total mass of monomers added during step (2) during the synthesis of the copolymer (W2) is from 0.2 to 4: 1.
22. dispersion according to claim 21, characterized in that the ratio of the total mass of monomers added when synthesizing the copolymer (W1) to the total mass of monomers added in step (2) when synthesizing the copolymer (W2) is 0.5-3.5: 1.
23. The dispersion according to claim 1, wherein the polymerization temperature in the polymerization of the synthetic copolymer (W1) is from 80 to 160 ℃,
in the polymerization reaction for synthesizing the copolymer (W2), the polymerization reaction temperature is 80 to 160 ℃,
the reaction temperature of the step (3) is 50-100 ℃, and the reaction time is 0.5-1.0 hour.
24. The dispersion as claimed in claim 23, wherein the polymerization temperature in the polymerization for the synthesis of the copolymer (W1) is 120-150 ℃; in the polymerization reaction for synthesizing the copolymer (W2), the polymerization reaction temperature is 120-150 ℃;
the reaction temperature of the step (3) is 60-90 ℃, and the reaction time is 0.5-1.0 hour.
25. The dispersion according to claim 1, wherein in the polymerization reaction for synthesizing the copolymer (W1), the monomers for each component are added dropwise for 2.0 to 5.0 hours, and the temperature is kept for 0.2 to 2.0 hours after the completion of the dropwise addition; in the step (2), the monomers of each component are added in a dropwise manner, the dropwise adding time of the monomers of each component is 0.5-2.0 hours, and the temperature is kept for 0.5-2.0 hours after the dropwise adding is finished.
26. The dispersion as claimed in claim 1, wherein an initiator is additionally added in the polymerization of the synthetic copolymer (W1) and in the polymerization of the synthetic copolymer (W2), and wherein, in the polymerization of the synthetic copolymer (W1), the amount of initiator added is from 0.5 to 4.0% by mass, based on the total mass of the components (A1) to (A5) added in step (1), and in the polymerization of the synthetic copolymer (W2), the amount of initiator added is from 0.5 to 4.0% by mass, based on the total mass of the components (A1) to (A5) added in step (2).
27. The dispersion as claimed in claim 26, wherein, in the polymerization of the synthetic copolymer (W1), the amount of initiator added is from 0.8 to 2.0% by mass of the total of the components (A1) to (A5) added in step (1), and in the polymerization of the synthetic copolymer (W2), the amount of initiator added is from 0.8 to 2.0% by mass of the total of the components (A1) to (A5) added in step (2).
28. Use of a chlorinated polypropylene/acrylate hybrid aqueous dispersion according to any one of claims 1 to 27 in aqueous coatings.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070129485A1 (en) * | 2005-12-07 | 2007-06-07 | Honda Motor Co., Ltd. | Water-base metallic coating for automotive interior materials and coated article |
| CN104987467A (en) * | 2015-07-20 | 2015-10-21 | 常州市武进晨光金属涂料有限公司 | Acrylate modified hydroxyl-terminated butadiene resin with low infrared emissivity, and preparation method thereof |
| CN108264643A (en) * | 2017-12-19 | 2018-07-10 | 万华化学（宁波）有限公司 | A kind of copolymer p, water-borne dispersions resin and its application in water paint |
| CN109280132A (en) * | 2018-09-06 | 2019-01-29 | 中国海洋石油集团有限公司 | Chlorinated polypropylene modified water-based acrylic resin with superior compatibility and preparation method thereof, application |
| CN109400815A (en) * | 2018-09-06 | 2019-03-01 | 中国海洋石油集团有限公司 | Chlorinated polypropylene modified acrylic acid resin and preparation method thereof with excellent ply adhesion |
| CN109438605A (en) * | 2018-09-17 | 2019-03-08 | 万华化学集团股份有限公司 | Water-soluble and aqueous dispersion type Hydroxylated acrylic resin and its preparation method and application |
-
2019
- 2019-12-23 CN CN201911334242.3A patent/CN113088153B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070129485A1 (en) * | 2005-12-07 | 2007-06-07 | Honda Motor Co., Ltd. | Water-base metallic coating for automotive interior materials and coated article |
| CN104987467A (en) * | 2015-07-20 | 2015-10-21 | 常州市武进晨光金属涂料有限公司 | Acrylate modified hydroxyl-terminated butadiene resin with low infrared emissivity, and preparation method thereof |
| CN108264643A (en) * | 2017-12-19 | 2018-07-10 | 万华化学（宁波）有限公司 | A kind of copolymer p, water-borne dispersions resin and its application in water paint |
| CN109280132A (en) * | 2018-09-06 | 2019-01-29 | 中国海洋石油集团有限公司 | Chlorinated polypropylene modified water-based acrylic resin with superior compatibility and preparation method thereof, application |
| CN109400815A (en) * | 2018-09-06 | 2019-03-01 | 中国海洋石油集团有限公司 | Chlorinated polypropylene modified acrylic acid resin and preparation method thereof with excellent ply adhesion |
| CN109438605A (en) * | 2018-09-17 | 2019-03-08 | 万华化学集团股份有限公司 | Water-soluble and aqueous dispersion type Hydroxylated acrylic resin and its preparation method and application |
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