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 2020-08-27 设计创作，主要内容包括：一水性聚合物,由聚烯烃基二醇改性的共聚物,并经由氨水、伯胺、仲胺、无机碱或上述的组合中和而成,其中所述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。(The water-based polymer is formed by neutralizing a polyolefin-based diol modified copolymer with ammonia water, primary amine, secondary amine, inorganic base or a combination of the ammonia water, the primary amine, the secondary amine and the inorganic base, wherein the copolymer is formed by copolymerizing an acid anhydride monomer with a double bond, a monomer with 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, an inorganic base, or a combination thereof,

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, 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, cumyl phenyl, cumyl ether, tert-butyl ether, benzoate, 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 30;

y is 3 to 9;

z is 1 to 5; and

m is 10 to 70.

3. The aqueous polymer of claim 2 wherein 0.1. ltoreq. z/(y + z). ltoreq.0.5.

4. The waterborne polymer of claim 1, having an acid number of between 40 and 300 mgKOH/g.

5. 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, an inorganic base, or a combination thereof,

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

6. The dispersion of claim 5, 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, cumyl phenyl, cumyl ether, tert-butyl ether, benzoate, 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 30;

y is 3 to 9;

z is 1 to 5; and

m is 10 to 70.

7. The dispersion as claimed in claim 5, wherein the average particle diameter of the pigment powder is between 280nm and 400 nm.

8. 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, an inorganic base, or a combination thereof,

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

9. The aqueous coating of claim 8, 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, cumyl phenyl, cumyl ether, tert-butyl ether, benzoate, 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 30;

y is 3 to 9;

z is 1 to 5; and

m is 10 to 70.

10. The aqueous coating of claim 8, wherein the average particle size of the pigment powder is between 280nm and 550 nm.

Technical Field

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

Background

In 2018, the global coating is sold to 5.7 million Taiwan coins, and the white coating with the largest sale amount accounts for about 50 percent. 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 a key problem in the failure of high tinting strength and high hiding power paints is that TiO is not popular₂The aqueous white color paste and the dispersant for coating are needed to be developed because the aqueous white color paste is easy to aggregate and settle, cannot be dispersed and stabilized, has poor compatibility with a binder and deteriorates the properties of the coating.

Disclosure of Invention

An embodiment of the present invention provides a waterborne polymer, comprising: the polyolefin-based diol modified copolymer is obtained by neutralizing ammonia water, primary amine, secondary amine, inorganic base or a combination of the ammonia water, the primary amine, the secondary amine and the inorganic base, wherein the copolymer is prepared by copolymerizing an acid anhydride monomer with a double bond, a monomer with 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: the polyolefin-based diol modified copolymer is obtained by neutralizing ammonia water, primary amine, secondary amine, inorganic base or a combination of the ammonia water, the primary amine, the secondary amine and the inorganic base, wherein the copolymer is prepared by copolymerizing an acid anhydride monomer with a double bond, a monomer with 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: the polyolefin-based diol modified copolymer is obtained by neutralizing ammonia water, primary amine, secondary amine, inorganic base or a combination of the ammonia water, the primary amine, the secondary amine and the inorganic base, wherein the copolymer is prepared by copolymerizing an acid anhydride monomer with a double bond, a monomer with 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 water-based polymer provided by the embodiment of the invention is prepared by neutralizing a polyolefin-based diol modified copolymer with ammonia water, primary amine, secondary amine, inorganic base or a combination of the ammonia water, the primary amine, the secondary amine and the inorganic base, wherein the copolymer is prepared by copolymerizing an acid anhydride monomer with a double bond, a monomer with a double bond and an 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: 3.2 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 polyethylene glycol monomethyl ether (MPEG), 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); r4 is H, C_1-4Alkyl or C_1-4Alkyl alcohol of (1); r⁵Is H, methyl, cumyl phenyl, cumyl ether, tert-butyl ether, benzoate, 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 isx is 8 to 30; y is 3 to 9; z is 1 to 5; and m is 10 to 70. 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.

In one embodiment, z/(y + z) ≦ 0.1, i.e., a grafting proportion 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 acid value of the waterborne polymer is between 40 and 300 mgKOH/g.

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/mole and 7500g/mole, can be between 7500g/mole and 9000g/mole, can be between 9000g/mole and 12000g/mole, or can be between 12000g/mole and 16000 g/mole. 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. The synthesis of the above-mentioned aqueous polymers is within the skill of one of ordinary skill in the art from available equipment and pharmaceuticals. 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. In one embodiment, a catalyst may be further added to promote the polymerization reaction, and the catalyst may be, for example, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, or hydrochloric acid. 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 1.0 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. The above-described polyolefin-based glycol-modified copolymer is then neutralized with aqueous ammonia, a primary amine, a secondary amine, an inorganic base, or a combination thereof, and is exemplified by the following:

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

the inorganic base can be potassium hydroxide (KOH), sodium hydroxide (NaOH), or sodium carbonate (Na)₂CO₃) Sodium bicarbonate (NaHCO)₃) Potassium carbonate (K)₂CO₃) Potassium bicarbonate (KHCO)₃) Barium carbonate (BaCO)₃) Barium hydroxide (Ba (OH)₂) Cesium hydroxide (CsOH) or cesium carbonate (Cs)₂CO₃)。

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 120cps at 1000 rpm. In addition, when the dispersion liquid is stored at room temperature for more than one year, the viscosity and the particle size of the pigment powder are maintained without being greatly changed, and it is apparent that the dispersion liquid has excellent stability.

In addition, the dispersion may be mixed with a binder, which may be a polyacrylic resin, a polyurethane resin, or a combination thereof, to form an aqueous 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 550 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. Briefly, the present invention provides aqueous polymers suitable for use as dispersants for pigment powders, and aqueous polymer-containing dispersions suitable for formulation into aqueous coatings.

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 polymers 1d 'and 1 d')

80g of styrene-maleic anhydride copolymer (b) are placed under nitrogen1000, 40mmole from Cray Valley) 120mL of Tetrahydrofuran (THF) were added, heated to 50 deg.C and stirred to dissolve completely1000. 192g of polyethylene glycol monomethyl ether (MPEG1200, 160mmole, from Mitsuka), in addition, were added to 100mL of THF and 100mL of n-butyl acetate, and the mixture was stirred with heating until the MPEG1200 was completely dissolved. Adding the MPEG1200 solution to the hot melt at 80 deg.C1000 for 22 hours. As described above1000 IR spectrum with maleic anhydride C ═ O signal (1778 cm)^-1). The intermediate product has a COOH signal (3444 cm) in the IR spectrum^-1)、CH₂Signal (2871 cm)^-1) And a C ═ O signal of an ester bond (1733 cm)^-1) And a C-O-C signal (1108 cm)^-1). From the IR spectra, MPEG1200 and1000 parts of maleic anhydride was subjected to a ring-opening addition reaction.

After removing the solvent by rotary concentration, 200g of the concentrate was added with 184g of water and 26g of aqueous ammonia (28%) and stirred until completely dissolved to obtain an aqueous polymer 1 d' (solid content: 48.8%) having an MPEG1200 graft ratio of about 45% and an acid value of about 100-120 mgKOH/g. The reaction is shown as the following formula, and x, y, z, m and A are respectively as follows according to the composition and the dosage of reactants: x is about 9 to 12, y is about 4 to 6, z is about 4, m is about 25 to 28 and A is about

In addition, 31g of water and 12g of triethanolamine were added to 40g of the concentrate, and the mixture was stirred until it was completely dissolved, thereby obtaining an aqueous polymer 1d "(solid content: 48.2%). The reaction is shown as the following formula, and x, y, z, m and A are respectively as follows according to the composition and the dosage of reactants: x is about 9 to 12, y is about 4 to 6, z is about 4, m is about 25 to 28, and A is about

Examples 1-2 (waterborne Polymer 2 d')

80g of1000(40mmole) was added to 220mL of Methyl Ethyl Ketone (MEK), and the mixture was stirred with heating until the mixture was completely dissolved1000. In addition, 320g of MPEG2000(160mmole, from the Mitsuki Synthesis) and 4g of p-toluenesulfonic acid (PTSA, 21mmole) were added to 200mL of MEK, and the mixture was stirred with heating until the MPEG2000 was completely dissolved. Adding the above MPEG 2000-containing solution to a reactor at 85 deg.C1000 for 9 hours in solution. After the solvent is removed by rotary concentration, 426g of water and 36g of ammonia water (28%) are added into the concentrate, and the mixture is stirred until the mixture is completely dissolved to obtain the dispersant such as the waterborne polymer 2 d' (solid content: 46.4%), the grafting proportion of the MPEG2000 is about 45%, and the acid value is about 65-85 mgKOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m and A are, according to the composition and amount of the reactants: x is about 9 to 12, y is about 4 to 6, z is about 4, and m is about 43 to 46 and A are about

Examples 1-3 (waterborne Polymer 3 d')

Under nitrogen, 40g of1000(20mmole) of MEK was added to 100mL of the solution, and the mixture was stirred with heating until the solution was completely dissolved1000. In addition, 342g of MPEG2000(171mmole) was added to 300mL of MEK, and the mixture was heated and stirred until the MPEG2000 was completely dissolved. Adding the above MPEG2000 solution to a temperature of 85 deg.C1000 solution after reaction for 9 hours. After the solvent is removed by rotary concentration, 466g of water and 18g of ammonia water (28%) are added into the concentrate, and the mixture is stirred until the mixture is completely dissolved, so that the waterborne polymer 3 d' (solid content: 44.1%) is obtained, the grafting proportion of the MPEG2000 is about 100%, and the acid value is about 20-40 mgKOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m and A are, according to the composition and amount of the reactants: x is about 9 to 12, y is about 0, z is about 8 to 10, m is about 43 to 46 and A is about

Examples 1-4 (waterborne Polymer 4 d')

150g of1000(75mmole) of MEK was added to 200mL of the solution, and the mixture was stirred with heating until the solution was completely dissolved1000. 225g of MPEG750(300mmole) and 3.75g of PTSA (19.7mmole) were additionally added to 300mL of MEK, and the mixture was heated and stirred until the MPEG750 was completely dissolved. Adding the above MPEG750 solution to the mixture at 80 deg.C1000 solution after reaction for 9 hours. After the solvent was removed by rotary concentration, 346g of water and 66g of ammonia (28%) were added to the concentrate, and the mixture was stirred until it was completely dissolved to obtain an aqueous polymer 4 d' (solid content: 47.9%), which was grafted with MPEG750 at a concentration of about 45%, and had an acid value of about 140 to 160 mgKOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m and A are, according to the composition and amount of the reactants: x is about 9 to 12, y is about 4 to 6, z is about 4, m is about 15 to 18 and A is about

Examples 1 to 5 (waterborne Polymer 5 d')

200g of1000(100mmole) of MEK was added thereto, and the mixture was stirred with heating until the MEK was completely dissolved1000. In addition, 150g of MPEG750(200mmole) and 3.50g of PTSA (18.4mmole) were added to 200mL of MEK, and heated with stirring until the MPEG750 was completely dissolved. Adding the above MPEG750 solution to the mixture at 80 deg.C1000 solution post reaction for 8 hours. After the solvent is removed by rotary concentration, 346g of water and 101g of ammonia water (28%) are added into the concentrate, and the mixture is stirred until the mixture is completely dissolved to obtain the waterborne polymer 5 d' (solid content: 44.2%), the grafting ratio of the MPEG750 is about 20%, and the acid value is about 235-255 mgKOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m and A are, according to the composition and amount of the reactants: x is about 9 to 12, y is about 6 to 8, z is about 2, m is about 15 to 18 and A is about

Examples 1 to 6 (waterborne Polymer 6 d')

Under nitrogen, 250g of1000(125mmole) of MEK was added thereto in an amount of 350mL, and the mixture was stirred with heating until complete dissolution1000. In addition, 150g of MPEG1200(125mmole) and 4.00g of PTSA (21.0mmole) were added to 200mL of MEK, and heated and stirred until the MPEG1200 was completely dissolved. Adding the above MPEG1200 solution to the mixture at 80 deg.C1000 solution post reaction for 8 hours. After the solvent is removed by rotary concentration, 378g of water and 136g of ammonia water (28%) are added into the concentrate, and the mixture is stirred until the mixture is completely dissolved, so that the waterborne polymer 6 d' (solid content: 44.0%) is obtained, the grafting of the MPEG1200 is about 10%, and the acid value is about 275-295 mgKOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m and A are, according to the composition and amount of the reactants: x is about 9 to 12, y is about 7 to 9, z is about 1, m is about 25 to 28 and A is about

Examples 1 to 7 (waterborne Polymer 7 d')

50g of2000(16.7mmole) 120mL MEK was added and stirred with heating until complete dissolution2000. 100g of MPEG2000(50mmole) and 1.50g of PTSA (7.89mmole) were additionally added to 120mL of MEK, and the mixture was stirred with heating until the MPEG2000 was completely dissolved. Adding the above MPEG2000 solution to the mixture at 80 deg.C2000 solution for 10 hours. After removing the solvent by rotary concentration, 50g of the concentrate was added with 60g of water and 6g of aqueous ammonia (28%) And stirring until the mixture is completely dissolved to obtain the waterborne polymer 7 d' (solid content: 43.1%) of MPEG2000 graft, and an acid value of about 90 to 110 mgKOH/g. The above reaction can be referred to the reaction formula of example 1-1, and x, y, z, m and A are, according to the composition and amount of the reactants: x is about 19 to 21, y is about 6 to 8, z is about 3, m is about 43 to 46 and A is about

Examples 1 to 8 (amphiphilic Polymer 8 d')

Under nitrogen, 30g of1000(15mmole) of MEK was added to 60mL of the solution, and the mixture was stirred with heating until the MEK was completely dissolved1000. Separately, 11g of MPEG750(15mmole, available from Zhongri synthesis) and 21g of dodecylamine (113mmole) were added to 60mL of MEK, and after stirring and heating until the MPEG750 and dodecylamine were completely dissolved, 0.6g of p-toluenesulfonic acid (3mmole) was added thereto. Adding the above solution of MPEG750, dodecylamine and p-toluenesulfonic acid at a temperature of 80 deg.C1000 solution, post reaction for 5 hours. After the solvent was removed by rotary concentration, 548g of water and 10g of aqueous ammonia (28%) were added to the concentrate, and the mixture was stirred until it was completely dissolved to obtain an amphiphilic polymer 8 d' (solid content: 10%). The reaction is shown as the following formula, and x, y, z', m and A are respectively as follows according to the composition and the dosage of reactants: x about 9 to 12, y about 0, z about 1, z' about 7 to 9, m about 15 to 18 and A about

Example 2-1 (aqueous Dispersion LAW348a)

Aqueous polymer 1 d' was taken as a dispersant, titanium dioxide powder (Kronos2360, available from Kronos, purity 92%) was stirred with water 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 LAW348 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 1 d' was 0.765 wt%, and the balance was water.

Example 2-2 (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.

Examples 2 to 3 (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 4 (aqueous dispersion LAW243a)

The aqueous polymer 2 d' was used as a dispersant, and titanium dioxide powder (Kronos2360) was pre-dispersed with water 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 LAW243 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 2 d' was 0.765 wt%, and the balance was water.

Examples 2 to 5 (aqueous dispersion LAW245a)

Taking the water-based polymer 3 d' as a dispersing agent, and stirring and pre-dispersing titanium dioxide powder (Kronos2360) and water. 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 LAW245 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 3 d' was 0.765 wt%, and the balance was water.

Examples 2 to 6 (aqueous dispersion LAW349a)

The aqueous polymer 1 d' 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 LAW349 a. In the above white slurry, titanium dioxide was 80 wt%, the aqueous polymer 1 d' was 0.4 wt%, and the balance was water.

Examples 2-7 (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 8 (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 9 (aqueous dispersion LAW282a)

The aqueous polymer 4 d' is taken as a dispersant, and titanium dioxide powder (Kronos2360) and water are 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 LAW282 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 4 d' was 0.765 wt%, and the balance was water.

Examples 2 to 10 (aqueous dispersion LAW284a)

Taking the aqueous polymer 5 d' as a dispersing agent, and stirring and pre-dispersing titanium dioxide powder (Kronos2360) and water. 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 LAW284 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 5 d' was 0.765 wt%, and the balance was water.

Examples 2 to 11 (aqueous dispersion LAW286a)

The aqueous polymer 6 d' was used as a dispersant, and titanium dioxide powder (Kronos2360) was pre-dispersed with water 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 LAW286 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 6 d' was 0.765 wt%, and the balance was water.

Examples 2 to 12 (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 13 (aqueous dispersions 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 14 (aqueous dispersion LAW308a)

The aqueous polymer 7 d' is taken as a dispersant, and titanium dioxide powder (Kronos2360) and water are 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 LAW308 a. In the above white slurry, titanium dioxide was 76.5 wt%, the aqueous polymer 7 d' was 0.765 wt%, and the balance was water.

Examples 2 to 15 (gel LAW331a)

Taking the amphiphilic polymer 8 d' as a dispersing agent, and stirring and pre-dispersing titanium dioxide powder (Kronos2360) and water. 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 was present (LAW331a) and could not be filtered through a 25 μm filter cloth. In the above gel, titanium dioxide was 76.5 wt%, amphiphilic polymer 8 d' was 0.765 wt%, and the balance was water.

The aqueous dispersions of the above examples were sampled and measured for average particle diameter (D)_ave)、D₉₅、D₁₀₀The viscosity at 1000rpm (temperature 25 ℃ C.) is shown in Table 1:

TABLE 1

From the above, the aqueous polymer dispersants 1d ', 2 d', 4d ', 5 d', 6d 'and 7 d' prepared in the embodiments of the present invention have better dispersing effects on titanium dioxide. The aqueous polymer dispersant 3 d' with higher grafting proportion prepared in the embodiment of the invention and the commercial dispersant have poorer effect on dispersing titanium dioxide (larger average particle size).

Example 3-1 (Water-borne white paint S86)

6.4g of the aqueous dispersion LAW348a were mixed with 13.6g of an acrylic binder (VSR-50 from Dow chemical) to a pigment volume concentration of 18%. Stirring at the rotation speed of 800-.

Example 3-2 (Water-borne white paint S87)

9.1g of the aqueous dispersion LAW348a 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 3 (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-.

Examples 3 to 4 (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 5 (Water-based 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 6 (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 7 (Water-borne white paint S88)

8.7g of the aqueous dispersion LAW348a 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 S89)

8.5g of the aqueous dispersion LAW348a were mixed with 11.5g of a polyacrylic binder (SP-3901, from the basic chemical company) to a pigment volume concentration of 28%. Stirring at the rotation speed of 800-.

Examples 3 to 9 (Water-based white paint S90)

8.7g of the aqueous dispersion LAW348a 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, in addition, Δ D in Table 2_aveThe percentage in parentheses in the column table is expressed as the change in the average particle size of the coating divided by the average particle size of the dispersion multiplied by 100.

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)

The aqueous white paint S87 (containing the dispersion LAW348a) and the aqueous white paint S14 (containing the commercially available white paste Kronos4311) were coated on a glass substrate with a No. 22 wire bar to form a wet film having a thickness of about 50.29 μm. 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 ZGM1120 to measure the gloss of the white film. The gloss of the white film formed by the water-based white paint S87 is 90.6, and the gloss of the white film formed by the water-based white paint S14 is 62.2, so that the gloss of the product can be effectively improved when the water-based polymer prepared by the embodiment 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 S86 (containing dispersion LAW348a), aqueous white paint S13 (containing commercial white slurry Kronos4311), aqueous white paint S87 (containing dispersion LAW348a), aqueous white paint S14 (containing commercial white slurry Kronos4311), aqueous white paint S35 (containing dispersion LAW294a) and aqueous white paint S36 (containing dispersion LAW295a) by 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 QEA IAS instrument. In the aqueous white paint having a pigment volume concentration of 18%, the reflectance (Y value) of the white film formed by the aqueous white paint S86 on the black substrate was 83.3, and the reflectance (Y value) on the white substrate was 90.5, which was the hiding ratio of 92.0%; the white film formed from the aqueous white paint S13 had a reflectance (Y value) on a black substrate of 82.0 and a reflectance (Y value) on a white substrate of 90.7, i.e., a hiding ratio of 90.4%. 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 S87 on the black substrate was 85.3, and the reflectance (Y value) on the white substrate was 91.1, that is, the hiding ratio was 93.6%; the white film formed from the aqueous white paint S14 had a reflectance (Y value) of 85.6 on a black substrate and a reflectance (Y value) of 91.9 on a white substrate, i.e., a hiding ratio of 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) on a black substrate of 84.1 and a reflectance (Y value) on a white substrate of 91.8, i.e., a hiding ratio of 91.6%. From the above, when the waterborne polymer prepared by the embodiment is used for a waterborne white coating, the coverage rate of the product can be effectively increased.

Example 6

The aqueous white paints S87, S14, S35 and S36 were applied to a 22-gauge wire rod to form films, 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 products with the aqueous polymer 1 d' prepared in the examples as dispersant (e.g. Δ YI) was lower, while the yellowing of the products with the commercially available dispersants BYK190 or BYK199 or the commercially available white pulp Kronos4311 was higher. For example, the Δ YI of the film formed from white coating S87 was 1.5 (belonging to 0-stage yellowing, no discoloration) after 1 hour of heating, and 5.5 (belonging to two-stage yellowing, slight discoloration) after 2 hours of heating; Δ YI of the film formed from white paint S14 was 4.6 (secondary yellowing, slight discoloration) after 1 hour of heating, and 14.7 (fifth yellowing, severe discoloration) after 2 hours of heating; 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); the Δ YI of the film formed from white coating S36 was 5.7 (secondary yellowing, slight discoloration) after 1 hour of heating, and 11.6 (quaternary yellowing, large 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 1d '(neutralized with aqueous ammonia) and the aqueous polymer 1 d' (neutralized with triethanolamine) were collected and the colors of both were transparent, clear and yellowish. When the former two are heated to 120 ℃ and maintained for 2 hours, the color of the waterborne polymer 1d 'is still transparent, clear and slightly yellow, but the color of the waterborne polymer 1 d' is changed to dark yellow. As can be seen from the above, tertiary amines are not suitable for forming the aqueous polymer described in the present application.

Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.