阅读说明：本技术 水性聚合物、分散液与水性涂料 (Aqueous polymer, dispersion and aqueous coating material ) 是由 张嘉文 余若涵 张信贞 陈佑蕙 陈贞伃 于 2019-11-13 设计创作，主要内容包括：一种水性聚合物,由：聚烯烃基二醇改性的共聚物,经由氨水、伯胺、仲胺或上述的组合中和而成,其中聚烯烃基二醇改性的共聚物由共聚物经由聚烯烃基二醇改性而成,以及其中共聚物由具有双键的酸酐单体、具有双键的单体与引发剂共聚而成。上述水性聚合物可与水及颜料粉体混合分散形成分散液。上述分散液可与粘合剂混合形成水性涂料。(An aqueous polymer consisting of: a polyolefin-based diol-modified copolymer neutralized with ammonia water, a primary amine, a secondary amine, or a combination thereof, wherein the polyolefin-based diol-modified copolymer is obtained by modifying a copolymer with a polyolefin-based diol, and wherein the copolymer is obtained by copolymerizing an acid anhydride monomer having a double bond, a monomer having a double bond, and an initiator. The aqueous polymer can be mixed and dispersed with water and pigment powder to form a dispersion liquid. The dispersion can be mixed with a binder to form an aqueous coating.)

1. An aqueous polymer consisting of:

a polyolefin-based diol-modified copolymer obtained by neutralizing with ammonia water, a primary amine, a secondary amine or a combination thereof,

wherein the polyolefin-based diol-modified copolymer is obtained by modifying a copolymer with a polyolefin-based diol, and

wherein the copolymer is formed by copolymerizing an anhydride monomer with double bonds, a monomer with double bonds and an initiator.

2. The waterborne polymer of claim 1, wherein the initiator comprises dibenzoyl peroxide, 2 '-azobisisobutyronitrile, di (t-butyl) peroxide, t-butyl peroxide, 1' -azo (cyanocyclohexane), 2, 5-dimethyl-2, 5-bis (t-butyl) hexane, t-butyl peroxybenzoate, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, or t-butyl peroxyacetate.

3. The waterborne polymer of claim 1, having the structure:

wherein R is¹Is H or methyl;

R²is C_6-12Aryl of (C)_3-12Heteroaryl of (A), C_2-10(ii) aliphatic hydrocarbyl, - (C ═ O) -OA, or a combination of the foregoing;

R³is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1);

R⁴is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1);

R⁵is H, methyl, phenyl, cumyl phenyl, cumyl ether, tert-butyl ether, benzoic acid, cyanocyclohexane, isobutyronitrile, C_2-11Alkyl of (C)_2-11Alkyl ester of (1), C_6-12Aryl of (C)_3-12Heteroaryl or C of_2-10An aliphatic hydrocarbon group of (1);

a is each independentlyOr H, and at least one A is

x is 8 to 21;

y is 3 to 9;

z is 1 to 5;

m is 10 to 70; and

n is 1 to 13.

4. The aqueous polymer of claim 3 wherein 0.1. ltoreq. z/(y + z). ltoreq.0.5.

5. The aqueous polymer of claim 1, having an acid number of between 40 and 250mg KOH/g.

6. A dispersion, comprising:

a water-borne polymer;

water; and

the pigment powder is prepared by mixing the following components,

wherein the aqueous polymer is prepared from:

a polyolefin-based diol-modified copolymer obtained by neutralizing with ammonia water, a primary amine, a secondary amine or a combination thereof,

wherein the polyolefin-based diol-modified copolymer is obtained by modifying a copolymer with a polyolefin-based diol, and

wherein the copolymer is formed by copolymerizing an anhydride monomer with double bonds, a monomer with double bonds and an initiator.

7. The dispersion of claim 6, wherein the aqueous polymer has the structure:

wherein R is¹Is H or methyl;

R²is C_6-12Aryl of (C)_3-12Heteroaryl of (A), C_2-10(ii) aliphatic hydrocarbyl, - (C ═ O) -OA, or a combination of the foregoing;

R³is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1);

R⁴is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1);

R³is H, methyl, phenyl, cumyl phenyl, cumyl ether, tert-butyl ether, benzoic acid, cyanocyclohexane, isobutyronitrile, C_2-11Alkyl of (C)_2-11Alkyl ester of (1), C_6-12Aryl of (C)_3-12Heteroaryl or C of_2-10An aliphatic hydrocarbon group of (1);

a is each independentlyOr H, and at least one A is

x is 8 to 21;

y is 3 to 9;

z is 1 to 5;

m is 10 to 70; and

n is 1 to 13.

8. The dispersion as claimed in claim 6, wherein the average particle diameter of the pigment powder is between 280nm and 400 nm.

9. An aqueous coating comprising:

a dispersion and a binder;

wherein the dispersion comprises:

a water-borne polymer;

water; and

the pigment powder is prepared by mixing the following components,

wherein the aqueous polymer is prepared from:

a polyolefin-based diol-modified copolymer obtained by neutralizing with ammonia water, a primary amine, a secondary amine or a combination thereof,

wherein the polyolefin-based diol-modified copolymer is obtained by modifying a copolymer with a polyolefin-based diol, and

wherein the copolymer is formed by copolymerizing an anhydride monomer with double bonds, a monomer with double bonds and an initiator.

10. The aqueous coating of claim 9, wherein the aqueous polymer has the structure:

wherein R is¹Is H or methyl;

R²is C_6-12Aryl of (C)_3-12Heteroaryl of (A), C_2-10(ii) aliphatic hydrocarbyl, - (C ═ O) -OA, or a combination of the foregoing;

R³is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1);

R⁴is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1);

R⁵is H, methyl, phenyl, cumyl phenyl, cumyl ether, tert-butyl ether, benzoic acid, cyanocyclohexane, isobutyronitrile, C_2-11Alkyl of (C)_2-11Alkyl ester of (1), C_6-12Aryl of (C)_3-12Heteroaryl or C of_2-10An aliphatic hydrocarbon group of (1);

a is each independentlyOr H, and at least one A is

x is 8 to 21;

y is 3 to 9;

z is 1 to 5;

m is 10 to 70; and

n is 1 to 13.

11. The aqueous coating of claim 9, wherein the average particle size of the pigment powder is between 280nm and 500 nm.

Technical Field

The present invention relates to aqueous polymers, and more particularly to dispersions and aqueous coatings comprising aqueous polymers.

Background

The worldwide paint sale in 2018 reaches 5.7 million Taiwan currencyThe most sold white paint is about 50%. With the improvement of environmental protection consciousness, the water-based white slurry is paid more attention and can be used for priming or color enhancement of color coatings. White paints require white pastes with high tinting strength and high hiding power (opacity), but the key problem with white pastes failing to make high tinting strength and high hiding power paints is that TiO is not popular₂The pigment is easy to aggregate and settle, cannot be dispersed and stabilized, and causes the property of the paint to be poor, so that the development of the water-based white color paste and the dispersant for the paint is needed.

Disclosure of Invention

An embodiment of the present invention provides a waterborne polymer, comprising: a polyolefin-based diol-modified copolymer neutralized with ammonia water, a primary amine, a secondary amine, or a combination thereof, wherein the polyolefin-based diol-modified copolymer is obtained by modifying a copolymer with a polyolefin-based diol, and wherein the copolymer is obtained by copolymerizing an acid anhydride monomer having a double bond, a monomer having a double bond, and an initiator.

An embodiment of the present invention provides a dispersion liquid including: a water-borne polymer; water; and pigment powder, wherein the aqueous polymer is prepared from: a polyolefin-based diol-modified copolymer neutralized with ammonia water, a primary amine, a secondary amine, or a combination thereof, wherein the polyolefin-based diol-modified copolymer is obtained by modifying a copolymer with a polyolefin-based diol, and wherein the copolymer is obtained by copolymerizing an acid anhydride monomer having a double bond, a monomer having a double bond, and an initiator.

An embodiment of the present invention provides a water-based paint, including: a dispersion and a binder; wherein the dispersion comprises: a water-borne polymer; water; and pigment powder, wherein the aqueous polymer is prepared from: a polyolefin-based diol-modified copolymer neutralized with ammonia water, a primary amine, a secondary amine, or a combination thereof, wherein the polyolefin-based diol-modified copolymer is obtained by modifying a copolymer with a polyolefin-based diol, and wherein the copolymer is obtained by copolymerizing an acid anhydride monomer having a double bond, a monomer having a double bond, and an initiator.

Detailed Description

The waterborne polymer provided by the embodiment of the invention can be used as a dispersing agent. The aqueous polymer can be mixed with water and pigment powder to form a dispersion. The dispersion can be mixed with a binder to form an aqueous coating.

The aqueous polymer provided by the embodiment of the invention is formed by neutralizing a polyolefin-based diol modified copolymer by ammonia water, primary amine, secondary amine or the combination of the ammonia water, the primary amine and the secondary amine, wherein the polyolefin-based diol modified copolymer is formed by modifying the copolymer by the polyolefin-based diol, and the copolymer is formed by copolymerizing an acid anhydride monomer with a double bond, a monomer with a double bond and an initiator (initiator). In one embodiment, the molar ratio of the anhydride monomer having a double bond to the monomer having a double bond may be 1: 2.3 to 1: 0.9. in one embodiment, the acid anhydride monomer having a double bond may be maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, or other suitable monomers. In one embodiment, the monomer having a double bond may be ethylene, propylene, isobutylene, methacrylic acid, acrylic acid, styrene, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, or other suitable monomers or combinations thereof. In one embodiment, the initiator may be dibenzoyl peroxide, 2 '-azobisisobutyronitrile, di (t-butyl) peroxide, t-butyl peroxide, 1' -azo (cyanocyclohexane), 2, 5-dimethyl-2, 5-bis (t-butyl) peroxide hexane, t-butyl peroxybenzoate, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, t-butyl peroxyacetate, or other suitable initiator. In one embodiment, the ratio of moles of polyolefin-based diol to moles of anhydride monomer is from 0.1: 1 to 0.5: 1. In one embodiment, the polyalkylene glycol may be a polyether monoamine, other suitable polyalkylene glycols, or combinations thereof. It is noted that if the polyolefin-based diol-modified copolymer is neutralized by a tertiary amine, the aqueous polymer may be significantly yellowed after heating, which may affect the color of the product.

In one embodiment, the structure of the aqueous polymer is:

wherein R is¹Is H or methyl; r²Is C_6-12Aryl of (C)_3-12Heteroaryl of (A), C_2-10(ii) aliphatic hydrocarbyl, - (C ═ O) -OA, or a combination of the foregoing; r³Is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1); r⁴Is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1); r⁵Is H, methyl, phenyl, cumyl phenyl, cumyl ether, tert-butyl ether, benzoic acid, cyanocyclohexane, isobutyronitrile, C_2-11Alkyl or C_2-11Alkyl ester of (1), C_6-12Aryl of (C)_3-12Heteroaryl or C of_2-10An aliphatic hydrocarbon group of (1); a is each independentlyOr H, and at least one A isx is 8 to 21; y is 3 to 9; z is 1 to 5; m is 10 to 70; and n is 1 to 13. If x is too low, the polymer is less likely to adsorb the pigment powder. If x is too high, the hydrophilicity of the polymer is deteriorated. If y is too low, the hydrophilicity of the polymer is deteriorated. If y is too high, the polymer cannot provide an effective steric hindrance. If z is too low, the hydrophilicity of the polymer is deteriorated. If z is too high, the amount of polymer-dispersed pigment powder required increases. If m is too low, no effective steric hindrance can be provided. If m is too high, the content of dispersible pigment powder is reduced. If n is too high, the hydrophilicity of the polymer is deteriorated.

In one embodiment, z/(y + z) ≦ 0.1, i.e., a graft ratio of 10% to 50%. If the proportion of z is too high, i.e. the grafting proportion of the polyolefin-based diol is too high, the water resistance of the coating layer containing this hydrophilic polymer is poor. If the ratio of z is too low, that is, if the graft ratio of the polyolefin-based diol is too low, the pigment powder cannot be dispersed effectively.

In one embodiment, the theoretical number average molecular weight (Mn) of the waterborne polymer is between 2500g/mole and 16000 g/mole. For example, the number average molecular weight of the waterborne polymer can be between 2500g/mol to 7500g/mol, can be between 7500g/mol to 9000g/mol, can be between 9000g/mol to 12000g/mol, or can be between 12000g/mol to 16000 g/mol. If the number average molecular weight of the aqueous polymer is too small or too large, the pigment powder cannot be dispersed effectively.

In one embodiment, the method for synthesizing the aqueous polymer is as follows. It should be noted that the following methods are only used for illustration and not for limiting the invention. One of ordinary skill in the art can synthesize the above-described waterborne polymers with pharmaceutical products using available equipment. First, an acid anhydride monomer having a double bond and a monomer having a double bond may be copolymerized in a solvent of cumyl benzene as an initiator to form a copolymer as shown below:

the polymerization mechanism is free radical polymerization, but the present application is not limited thereto. For example, one of ordinary skill in the art can use other initiators for free radical polymerization, or other polymerization mechanisms such as Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization or other feasible polymerization mechanisms. The above copolymers may be block, alternating or random copolymers. In some embodiments, commercially available copolymers can be purchased directly without the need for self-synthesis.

The copolymers described above (e.g., grafted to the copolymer) may then be modified with a polyolefin-based diol, as shown below:

in the above formula, the repeating units corresponding to x, y and z are arranged alternately or randomly, not in blocks. Generally speaking, the grafting dispersity of the polyolefin-based diol in the embodiment of the invention is uniform, which is beneficial to uniform dispersion of pigment powder. For example, the PDI (Mw/Mn) of the formed waterborne polymer is between 1.3 and 2.0. If the PDI of the aqueous polymer is too high, it means that the grafting sites of the polyolefin-based diol are too uneven, which is disadvantageous for subsequent dispersion applications.

Then, the above-mentioned polyolefin-based diol-modified copolymer is neutralized with ammonia, a primary amine, a secondary amine or a combination thereof as follows:

it is noted that there may be portions of A that remain H, rather thanIn other words, not all-COOH groups are neutralizedAnd NH₂(R³)

The polymer can be used for dispersing pigment powder. For example, the dispersion liquid according to an embodiment of the present invention may include the above-mentioned aqueous polymer, water, and pigment powder. In one embodiment, the pigment powder may comprise between 70 wt% and 81 wt% of the dispersion. If the proportion of the pigment powder is too high, the viscosity of the dispersion liquid becomes too high and the solvent becomes too small and tends to dry out, so that the pigment powder is precipitated. If the proportion of the pigment powder is too low, the practicability of the product is lowered. In one embodiment, the weight ratio of the effective components of the pigment powder and the aqueous polymer may be between 100: 0.4 and 100: 3, such as between 100: 0.4 and 100: 1 or between 100: 1 and 100: 3. If the proportion of the aqueous polymer is too low, the pigment powder cannot be dispersed effectively. If the proportion of the aqueous polymer is too high, the cost increases if the pigment powder cannot be further dispersed. In the dispersion, the average particle size of the pigment powder may be between 280nm and 400 nm. Generally, the smaller the average particle diameter of the pigment powder, the better. In addition, the viscosity of the dispersion may be between 30cps and 100cps at 1000 rpm. In addition, the viscosity of the dispersion liquid and the particle size of the pigment powder were maintained without being significantly changed even when the dispersion liquid was stored at room temperature for more than half a year, and it was apparent that the stability of the dispersion liquid was excellent.

In addition, the dispersion may be mixed with a binder, which may be a polypropylene resin, a polyurethane resin, or a combination thereof, to form a water-borne coating. In one embodiment, the weight ratio of the dispersion to the binder may be between 30: 70 and 55: 45. If the proportion of the binder is too low, the adhesion of the pigment powder is deteriorated. If the proportion of the binder is too high, the pigment powder properties are not readily revealed. For example, commercially available binders such as VSR-50 (available from Dow chemical), ESP-2293 (available from ESP materials), SP3901 (available from basic chemical) and 2026c (available from Hexa and Chemicals) can be mixed with the dispersion to form an aqueous coating. In the water-based paint, the Pigment Volume Concentration (PVC) of the pigment powder may be between 15% and 30%. If the proportion of the pigment powder is too low, the hiding ratio decreases. If the proportion of the pigment powder is too high, the gloss of the paint is deteriorated. In the water paint, the average particle size of the pigment powder can be between 280nm and 500 nm. Generally, if the average particle size of the pigment powder in the aqueous coating material is much larger than the average particle size of the pigment powder in the dispersion, the compatibility between the dispersant (e.g., aqueous polymer) and the binder is poor. In some embodiments, the difference between the average particle size of the pigment powder in the aqueous coating material and the average particle size of the pigment powder in the dispersion may be less than 5%.

The water-based paint is dried to form a film after being coated on a substrate, and has excellent glossiness and hiding performance. On the other hand, the aqueous polymer has a low degree of yellowing after heating at a high temperature. In short, the aqueous polymer provided by the invention is suitable for being used as a dispersant of pigment powder, and the dispersion liquid containing the aqueous polymer is suitable for being prepared into an aqueous coating.

In the above examples, the pigment powder is mainly titanium dioxide powder, which is a common white pigment. However, the aqueous polymer of the present invention is not limited to dispersed titanium dioxide. For example, the pigment powder may be a yellow pigment such as cadmium yellow (PY35, C.I.77205, CAS #12237-67-1), titanium nickel yellow (PY53, C.I.77788, CAS #8007-18-9), praseodymium zirconium yellow (PY159, C.I.77997, CAS #68187-15-5), chromium titanium yellow (PY162, C.I.77896, CAS # 68611-42-7; PY163, C.I.77897, CAS #68186-92-5), or bismuth yellow (PY184, C.I.771740, CAS # 14059-33-7). The pigment powder can be magenta pigment such as iron red (PR101, C.I.77491, CAS #1317-60-8), cadmium red (PR108, C.I.77202, CAS #58339-34-7), lead chromium red (PR104, C.I.77605, CAS # 12656-85-8; PR105, C.I.77578, CAS #1314-41-6) or iron zirconium red (PR232, C.I.77996, CAS # 68412-79-3). The pigment powder can be cyan pigment such as cobalt blue (PB28, C.I.77364, CAS #68187-40-6) and cobalt chromium blue (PB36, C.I.77343, CAS # 68187-11-1). The pigment powder can be black pigment such as manganese iron black (PBK26, C.I.77494, CAS # 68186-94-7; PBK33, C.I.77537, CAS #75864-23-2), cobalt iron chromium black (PBK27, C.I.77502, CAS #68186-97-0), copper chromium black (PBK28, C.I.77428, CAS #68186-91-4), chrome iron black (PBK30, C.I.77504, CAS #71631-15-7) or titanium black (PBK35, C.I.77890, CAS # 70248-09-8). The pigment powder can be white inorganic pigment such as titanium white (PW6, C.I.77891, CAS #13463-67-7), zirconium white (PW12, C.I.77990, CAS #1314-23-4) or zinc white (PW4, C.I.77947, CAS # 1314-13-2). The pigment powder can be orange pigment such as cadmium orange (PO20, C.I.77199, CAS #12656-57-4) and orange chrome yellow (PO21, C.I.77601, CAS # 1344-38-3). The pigment powder can be green pigment such as chromium green (PG17, C.I.77288, CAS #1308-38-9), cobalt green (PG19, C.I.77335, CAS #8011-87-8), cobalt chromium green (PG26, C.I.77344, CAS #68187-49-5) or cobalt titanium green (PG50, C.I.77377, CAS # 68186-85-6). The pigment powder may also be other suitable pigments without being limited to the above pigments.

In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below:

[ examples ]

Example 1-1 (waterborne Polymer 1d)

Under nitrogen, 79g of(26mmole from Cray Valley) 200mL of MEK were added and stirred with heating until completely dissolved. 494g of a polyether monoamine (A)L-207, 247mmole from Huntsman) was added to 100mL of MEK and the mixture was heated at 85 deg.CL-207 is added toThe reaction was then continued for 12 hours. After removing the solvent by rotary concentration, 912g of water and 16g of aqueous ammonia (28%) were added to the concentrate, and the mixture was stirred until it was completely dissolved to obtain a dispersant such as an aqueous polymer 1d (solid content: 38.4%), which was an aqueous polymerThe grafting proportion of the L-207 is 100 percent, and the acid value is about 20-40 mg KOH/g. The reaction is shown as the following formula, and x, y, z, m, n and A are respectively as follows according to the composition and the dosage of reactants: x is about 19 to 21, y is about 0, z is about 9 to 11, m is about 30 to 32, n is about 10 to 12 and A isAs described aboveHas a C ═ O signal of maleic anhydride in the IR spectrum (1778 cm)^-1). The IR spectrum of the intermediate product has NH, COOH signals (3463 cm)^-1)、CH₂Signal (2881 cm)^-1) C ═ O signal for amide bond (1643 cm)^-1) And C-O-C signal (1103 cm)^-1). As can be seen from the above-mentioned IR spectrum,l-207 andthe maleic anhydride of (2) is subjected to a ring-opening addition reaction.

Examples 1 to 2 (Water-based Polymer 2d)

80g of(40mmole from Cray Valley) 200mL of THF were added and stirred with heating until completely dissolved. 120g of a polyether monoamine (A)L-300, 40mmole from Huntsman) was added 100mL of THF and the mixture was heated at 50 deg.CL-300 is added toThe reaction was continued for 18 hours. After removing the solvent by rotary concentration, 168g of water and 43g of aqueous ammonia (28%) were added to the concentrate, and the mixture was stirred until it was completely dissolved to obtain a dispersant such as an aqueous polymer 2d (solid content: 48.7%) which was a dispersion ofThe grafting content of the L-300 is about 10 percent, and the acid value is about 170-190 mg KOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m, n and A are, respectively: x is about 9 to 12, y is about 7 to 9, z is about 1, m is about 57 to 60, n is about 7 to 9 and A is

Examples 1 to 3 (Water-based Polymer 3d)

50g of(25mmole) 100mL of THF was added and stirred with heating until completely dissolved100g of a polyether monoamine (A)L-200, 50mmole from Huntsman) 70mL of THF were added and stirred with heating until complete dissolutionL-200. At 50 ℃ willL-200 solution is added toThe solution was post-reacted for 18 hours. Then, after removing the solvent by rotary concentration, 121g of water and 17g of aqueous ammonia (28%) were added to the concentrate, and the mixture was stirred until it was completely dissolved to obtain an aqueous polymer 3d (solid content: 52.0%) which was an aqueous polymerThe grafting proportion of the L-200 is about 20 percent, and the acid value is about 130-150 mg KOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m, n and A are, respectively: x is about 9 to 12, y is about 6 to 8, z is about 2, m is about 39 to 42, n is about 2 to 4 and A is

Examples 1 to 4 (Water-based Polymer 4d)

80g of(40mmole) 100mL of THF was added and stirred with heating until completely dissolvedAn additional 80gL-100(80mmole) was added to 100mL of THF, and the mixture was stirred with heating until the solution was completely dissolvedL-100. At 50 ℃ willL-100 solution is added toThe solution was post-reacted for 18 hours. After removing the solvent by rotary concentration, 139g of water and 31g of aqueous ammonia (28%) were added to the concentrate, and the mixture was stirred until it was completely dissolved to obtain an aqueous polymer 4d (solid content: 48.5%), which wasThe grafting proportion of the L-100 is about 20 percent, and the acid value is about 200-220 mg KOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m, n and A are, respectively: x is about 9 to 12, y is about 6 to 8, z is about 2, m is about 18 to 21, n is about 2 to 3 and A is

Examples 1-5 (waterborne polymers 5d and 5 d')

200g of(100mmole) 200mL MEK was added and stirred with heating until completely dissolvedAnother 300gL-100(300mmole) was added to 100mL of MEK, and the mixture was stirred with heating until complete dissolutionL-100. At 50 ℃ willL-100 solution is added toThe solution was post-reacted for 18 hours. After the solvent was removed by rotary concentration, 300g of the concentrate was added with 303g of water and 56g of aqueous ammonia (28%), and stirred until it was completely dissolved to obtain an aqueous polymer 5d (solid content: 45.5%) which was a solid contentThe grafting proportion of the L-100 is about 30 percent, and the acid value is about 150 to 170 mgKOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m, n and A are, respectively: x is about 9 to 12, y is about 5 to 7, z is about 3, m is about 18 to 21, n is about 2 to 3 and A is

In addition, 67g of water and 46g of triethanolamine were added to 100g of the concentrate, and the mixture was stirred until it was completely dissolved, thereby obtaining an aqueous polymer 5d "(solid content: 47.0%). The reaction is shown as the following formula, and x, y, z, m, n and A are respectively as follows according to the composition and the dosage of reactants: x is about 9 to 12, y is about 5 to 7, z is about 3, m is about 18 to 21, n is about 2 to 3 and A is

Example 2-1 (aqueous Dispersion LAW294a)

A commercially available dispersant Disperbyk-190 (from BYK), titanium dioxide powder (Kronos2360) and water were stirred for predispersion. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW294 a. In the above white slurry, titanium dioxide was 76.5 wt%, a commercially available dispersant Disperbyk-190 was 0.765 wt%, and the balance was water.

Example 2-2 (aqueous Dispersion LAW295a)

A commercially available dispersant Disperbyk-199 (from BYK) and titanium dioxide powder (Kronos2360) were pre-dispersed with water under stirring. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW295 a. In the above white slurry, titanium dioxide was 76.5 wt%, a commercially available dispersant Disperbyk-199 was 0.765 wt%, and the balance was water.

Examples 2 to 3 (aqueous dispersion LAW247a)

The aqueous polymer 1d was taken as a dispersant, and titanium dioxide powder (Kronos2360) was stirred with water to predisperse. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW247 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 1d was 0.765 wt%, and the balance was water.

Examples 2-4 (gel LAW261a)

A commercially available dispersant Disperbyk-190 (from BYK), titanium dioxide powder (Kronos2360) and water were stirred for predispersion. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. After shaking was complete, the gel (LAW261a) was not filterable with a 25 μm filter cloth. In the above gel, titanium dioxide was 80 wt%, a commercially available dispersant Disperbyk-190 was 0.4 wt%, and the balance was water.

Examples 2 to 5 (gel LAW263a)

A commercially available dispersant Disperbyk-199 (from BYK) and titanium dioxide powder (Kronos2360) were pre-dispersed with water under stirring. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. After shaking was complete, the gel (LAW263a) was not filtered through a 25 μm filter cloth. In the above gel, titanium dioxide was 80 wt%, the commercially available dispersant Disperbyk-199 was 0.4 wt%, and the balance was water.

Examples 2 to 6 (aqueous dispersion LAW289a)

The aqueous polymer 2d was used as a dispersant, and titanium dioxide powder (Kronos2360) was stirred with water to be predispersed. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW289 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 2d was 0.765 wt%, and the balance was water.

Examples 2 to 7 (aqueous dispersion LAW273a)

Taking a commercially available dispersant Solsperse^TM20000 (from Lubrizol), titanium dioxide powder (Kronos2360) and water were pre-dispersed by stirring. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW273 a. In the white slurry, the titanium dioxide accounts for 76.5 wt%, and the commercial dispersant Solsperse^TM20000 is 0.765 wt%, and the rest is water.

Examples 2 to 8 (aqueous dispersion LAW290a)

The aqueous polymer 3d was taken as a dispersant, and titanium dioxide powder (Kronos2360) was stirred with water to predisperse. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW290 a. In the above white slurry, titanium dioxide was 76.5 wt%, aqueous polymer 3d was 0.765 wt%, and the balance was water.

Examples 2 to 9 (aqueous dispersion LAW292a)

The aqueous polymer 4d was taken as a dispersant, and titanium dioxide powder (Kronos2360) was stirred with water to predisperse. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW292 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 4d was 0.765 wt%, and the balance was water.

Examples 2 to 10 (aqueous dispersion LAW293a)

Taking a commercially available dispersantUltra PX 4575 (from BASF), titanium dioxide powder (Kronos2360) and water were pre-dispersed by stirring. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW293 a. In the above white slurry, titanium dioxide was 76.5 wt%, and a commercially available dispersant was usedUltra PX 4575 comprised 0.765 wt% and the balance water.

Examples 2 to 11 (aqueous dispersion LAW346a)

The aqueous polymer 5d was used as a dispersant, and titanium dioxide powder (Kronos2360) was stirred with water to predisperse. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. After shaking, the mixture was filtered through a 25 μm filter cloth to obtain a white slurry such as aqueous dispersion LAW346 a. In the above white slurry, titanium dioxide was 76.5 wt%, water-based polymer 5d was 0.765 wt%, and the balance was water.

Examples 2 to 12 (aqueous dispersion LAW353a)

The aqueous polymer 5d was used as a dispersant, and titanium dioxide powder (Kronos2360) was stirred with water to predisperse. After adding the zirconium beads, the mixture was placed in a LAU mill and dispersed at room temperature for 8 hours with shaking. Filtering with 25 μm filter cloth after shaking to obtain white slurry such as aqueous dispersion LAW353 a. In the above white slurry, titanium dioxide was 80.0 wt%, the aqueous polymer 5d was 0.4 wt%, and the balance was water.

The average particle diameter (D) of the aqueous dispersion of the above example was measured_ave)、D₉₅、D₁₀₀The viscosity at 1000rpm (temperature 25 ℃ C.) is shown in Table 1:

TABLE 1

From the above, the aqueous polymer dispersants 2d, 3d, 4d and 5d with low grafting ratio prepared in the embodiment of the present invention have better dispersing effect on titanium dioxide. The aqueous polymer dispersant 1d and the commercially available dispersant prepared in the examples of the present invention, which have a high graft ratio, have a poor dispersion effect (a large average particle size) on titanium dioxide.

Example 3-1 (Water-borne white paint S13)

6.6g of a commercially available white pulp Kronos4311 were mixed with 13.4g of a binder VSR-50, the pigment volume concentration of which was 18%. Stirring at the rotation speed of 800-.

Example 3-2 (Water-borne white paint S14)

9.4g of a commercially available white pulp Kronos4311 were mixed with 10.6g of a binder VSR-50, the pigment volume concentration of which was 28%. Stirring at the rotation speed of 800-.

Examples 3 to 3 (Water-borne white paint S35)

9.3g of the aqueous dispersion LAW294a were mixed with 10.7g of the binder VSR-50, the pigment volume concentration of which was 28%. Stirring at the rotation speed of 800-.

Examples 3 to 4 (Water-borne white paint S36)

9.3g of the aqueous dispersion LAW295a were mixed with 10.7g of the binder VSR-50, the pigment volume concentration of which was 28%. Stirring at the rotation speed of 800-.

Examples 3 to 5 (Water-based white paint S80)

6.4g of the aqueous dispersion LAW346a were mixed with 13.6g of an acrylic binder VSR-50, the pigment volume concentration of which was 18%. Stirring at the rotation speed of 800-.

Examples 3 to 6 (Water-borne white paint S81)

9.1g of the aqueous dispersion LAW346a were mixed with 10.9g of the binder VSR-50, the pigment volume concentration of which was 28%. Stirring at the rotation speed of 800-.

Examples 3 to 7 (Water-borne white paint S82)

8.7g of the aqueous dispersion LAW346a were mixed with 11.3g of a polyacrylic acid binder (ESP-2293, from ESP materials) to a pigment volume concentration of 28%. Stirring at the rotation speed of 800-.

Examples 3 to 8 (Water-borne white paint S83)

8.5g of the aqueous dispersion LAW346a were mixed with 11.5g of a polyacrylic binder (SP-3901, from R.C.) to a pigment volume concentration of 28%. Stirring at the rotation speed of 800-.

Examples 3 to 9 (Water-based white paint S84)

8.7g of the aqueous dispersion LAW346a were mixed with 11.3g of a polyurethane binder (2026C, from Liu Kao and Chemicals) to give a pigment volume concentration of 28%. Stirring at the rotation speed of 800-.

The viscosity of the above aqueous white paint at 1000rpm (temperature 25 ℃ C.) and the average particle diameter (D) of titanium dioxide in the paint_ave) As shown in table 2.

TABLE 2

The dispersion of the aqueous polymer dispersant prepared in the examples was mixed with a binder resin to form a coating material, and the average particle size of titanium dioxide particles in the coating material was not increased significantly as compared with the commercially available white slurry.

Example 4 (gloss comparison)

A wet film having a thickness of about 50.29 μm was formed by applying an aqueous white paint S14 (containing commercially available white paste Kronos4311) and an aqueous white paint S81 (containing dispersion LAW346a) to a glass substrate with a No. 22 wire bar. Drying the wet film to obtain the white film. The above white film was irradiated with 60 degrees of incident light in a gloss meter ZEHNTNER ZGM 1120 to measure the gloss of the white film. The gloss of the white film formed by the water-based white paint S81 is 86.4, while the gloss of the white film formed by the water-based white paint S14 is 62.2, and the gloss of the product can be effectively increased when the water-based polymer prepared by the embodiment of the invention is used for the water-based white paint.

Example 5 (coverage comparison)

A BYK-coated paper (model: PA-2814) was coated with aqueous white paint S13 (containing commercial white pulp Kronos4311), S80 (containing dispersion LAW346a), aqueous white paint S14 (containing commercial white pulp Kronos4311), S35 (containing dispersion LAW294a), aqueous white paint S36 (containing dispersion LAW295a) and S81 (containing dispersion LAW346a) by a No. 22 wire rod to form a wet film having a thickness of about 50.29 μm. Drying the wet film to obtain the white film. The hiding ratio of the white film was measured according to ASTM D2805 in an image analyzer QEAAS instrument. In the aqueous white paint having a pigment volume concentration of 18%, the reflectance (Y value) of the white film formed from the aqueous white paint S13 on the black substrate was 82.0, and the reflectance (Y value) on the white substrate was 90.7, that is, the hiding ratio was 90.4%; the white film formed from the aqueous white paint S80 had a reflectance (Y value) on a black substrate of 84.0 and a reflectance (Y value) on a white substrate of 90.6, i.e., a hiding ratio of 92.7%. In the aqueous white paint having a pigment volume concentration of 28%, the reflectance (Y value) of the white film formed from the aqueous white paint S14 on the black substrate was 85.6, and the reflectance (Y value) on the white substrate was 91.9, that is, the hiding ratio was 93.1%; the white film formed from the aqueous white paint S35 had a reflectance (Y value) on a black substrate of 84.6 and a reflectance (Y value) on a white substrate of 91.5, i.e., a hiding ratio of 92.5%; the white film formed from the aqueous white paint S36 had a reflectance (Y value) of 84.1 on a black substrate and a reflectance (Y value) of 91.8 on a white substrate, i.e., a hiding ratio of 91.6%; the white film formed from the aqueous white paint S81 had a reflectance (Y value) of 85.7 on a black substrate and a reflectance (Y value) of 91.4 on a white substrate, i.e., a hiding ratio of 93.8%. From the above, when the waterborne polymer prepared by the embodiment of the invention is used for a waterborne white coating, the coverage rate of the product can be effectively increased.

Example 6

The aqueous white paints S14, S35, S36 and S81 were applied to a glass substrate with a 22-gauge wire rod, and then the chromaticity coordinates (X, Y, Z) were measured. The film was then heated to 210 ℃ for 1 and 2 hours, respectively, and the chromaticity coordinates of the film were measured. The yellowing of the product with the waterborne polymer 5d prepared in the example as a dispersant (e.g., Δ YI) was lower, while the yellowing of the product with the commercially available dispersant BYK190 or BYK199 or the commercially available white pulp Kronos4311 was higher. For example, the Δ YI after 1 hour heating of the film formed from white paint S14 was 4.6 (secondary yellowing, slight discoloration), and after 2 hours heating was 14.7 (fifth yellowing, severe discoloration); Δ YI after 1 hour of heating of the film formed from white paint S35 was 2.5 (primary yellowing, very slight discoloration), and Δ YI after 2 hours of heating was 7.5 (tertiary yellowing, significant discoloration); Δ YI of the film formed from white paint S36 was 5.7 (secondary yellowing, slight discoloration) after 1 hour of heating, and Δ YI of 11.6 (quaternary yellowing, large discoloration) after 2 hours of heating; the Δ YI of the film formed from white coating S81 was 1.3 (belonging to 0-stage yellowing, no discoloration) after 1 hour of heating, and was 5.4 (belonging to two-stage yellowing, slight discoloration) after 2 hours of heating. Δ YI (Yellow difference) is defined as follows: YI ═ 100 (1.30X-1.13Z)/Y, Δ YI ═ YI after heating-YI before heating. Delta YI is less than or equal to 1.5, represents no color change and belongs to the 0 grade; delta YI is more than 1.6 and less than or equal to 3.0, which represents very slight color change and belongs to grade 1; delta YI is more than 3.1 and less than or equal to 6.0, represents slight discoloration and belongs to grade 2; delta YI is more than 6.1 and less than or equal to 9.0, which represents obvious color change and belongs to grade 3; delta YI is more than 9.1 and less than or equal to 12.0, which represents large color change and belongs to 4 grades; 12.1 < DeltaYI, representing severe discoloration, grade 5.

Example 7 (comparison of neutralizing Agents)

The aqueous polymer 5d (neutralized with ammonia water) and the aqueous polymer 5d "(neutralized with triethanolamine) were collected and the colors of both were transparent, clear and yellowish. After heating the two above-mentioned materials to 120 deg.C and maintaining them for 2 hr, the colour of the aqueous polymer 5d still is transparent, clear and yellowish, but the colour of the aqueous polymer 5d "is changed into deep yellow. As is apparent from the above, tertiary amines are not suitable for forming the aqueous polymer of the present invention.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.