CN111647105B

CN111647105B - Carboxylic acid vinyl ester copolymer and preparation method thereof

Info

Publication number: CN111647105B
Application number: CN202010303728.7A
Authority: CN
Inventors: 李乐; 马鹏飞
Original assignee: Sun Yat Sen University
Current assignee: Sun Yat Sen University
Priority date: 2020-04-16
Filing date: 2020-04-16
Publication date: 2021-09-14
Anticipated expiration: 2040-04-16
Also published as: CN111647105A

Abstract

The present invention relates to a process for converting polyvinyl ketones and copolymers thereof into polyvinyl carboxylate copolymers. The conversion rate of vinyl ketone structural units in the initial polymer can be adjusted at will, and the chain scission phenomenon in the reaction process is also greatly inhibited. By adopting the post-polymerization modification method of the invention after the vinyl ketone and other high-activity monomers are copolymerized, the problem of large reactivity ratio difference between the vinyl carboxylate low-activity monomer and the high-activity monomer can be avoided, and the copolymer of the vinyl carboxylate and other high-activity monomers with any proportion can be obtained. The modified polyvinyl acetate prepared by the method is expected to overcome the defects of poor water resistance, heat resistance, mechanical stability and other physical and chemical properties of the traditional polyvinyl acetate latex, and greatly widens the variety range of the current polyvinyl acetate latex. In addition, the proportion of the carboxylic acid vinyl ester monomer unit in the polymer prepared by the method is controllable, so that the controllable photodegradability of the copolymer is realized.

Description

Carboxylic acid vinyl ester copolymer and preparation method thereof

Technical Field

The invention relates to a carboxylic acid vinyl ester copolymer and a preparation method thereof.

Background

Radical polymerization plays an extremely important role in polymer chemistry. A large proportion of commercial polymers are obtained by free radical polymerization, such as low density polyethylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polymethyl acrylate, polytetrafluoroethylene, etc. Although the number of radical monomers currently used in industry is limited, the variety of radical polymers is greatly expanded because different radical monomers can be copolymerized to obtain different copolymers.

However, conventional radical polymerization suffers from a series of problems, mainly including side reactions or inhibition of polymerization caused when the monomers contain reactive groups or inhibition groups, and reactivity ratio problems in the copolymerization of high-active radical monomers and low-active radical monomers, resulting in that some monomers, for example, low-active monomers such as vinyl acetate, cannot form copolymers by radical polymerization.

Polyvinyl acetate is used as a base material for paints, adhesives, papers, chewing gums and textile finishing agents, and is a raw material for polyvinyl alcohol and polyvinyl acetal, which can be spun into vinylon, and has a high value in industry. For example, polyvinyl acetate latex has the characteristics of environmental friendliness, high bonding strength, excellent mechanical stability, resistance to microbial corrosion, certain resistance to oxidation and ultraviolet radiation, and the like. However, the conventional polyvinyl acetate latex has disadvantages such as poor water resistance, heat resistance and mechanical stability; the bonding strength is reduced under the damp and hot conditions; the creep resistance is poor, and the rubber skin is easy to slide under the action of long-term load or high temperature; poor storage stability due to latex stability, and the like. Therefore, it is necessary to modify polyvinyl acetate, for example, by blending modification and copolymerization modification. Due to compatibility problems, blending modification often leads to phase separation and poor stability. The copolymerization modification method is mainly limited by using vinyl acetate as a low-activity monomer, and a copolymer cannot be obtained due to the fact that the vinyl acetate has a large reactivity ratio difference with most high-activity monomers, for example, a styrene monomer with a large reactivity ratio difference with the vinyl acetate is actually a polymerization inhibitor of the styrene monomer. There is therefore a need for new processes for the preparation of vinyl acetate copolymers.

Disclosure of Invention

The invention aims to provide a vinyl carboxylate copolymer and a preparation method thereof. The vinyl carboxylate ester comprises vinyl acetate or other low activity vinyl carboxylate ester. The invention adopts polyvinyl ketone and copolymer thereof as raw materials, and can obtain copolymer of vinyl carboxylate and various high-activity free radical monomers, such as random copolymer or block copolymer, by oxidation under specific conditions.

Specifically, the invention provides a carboxylic acid vinyl ester copolymer, the structural formula of which is shown as formula II:

wherein a, b, c and n represent the degree of polymerization of the respective repeating units, and are integers of 0 to 100000, preferably 0 to 50000, more preferably 0 to 10000, most preferably 0 to 1000, but a and b are not zero, and a is greater than or equal to b + c; b + n is greater than 10, preferably greater than 50, more preferably greater than 100; (b + c) (a-b-c) is greater than 20:80, preferably greater than 30:70, more preferably greater than 40:60, most preferably greater than 50: 50; a. b, c and n may be, independently of each other, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 960, 940, 950, 970, 980, 1000, 980, 990, 5000, 3000, 990, 6000, 8000, 90000, 7000, 50000, 7000, 50000, 20000, 50000.

Wherein R1 is selected from the group consisting of C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C3-C10, preferably C3-C8, more preferably C3-C5 cycloalkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl; r2 is alkyl of H, F, Cl or C1-C10, preferably C1-C5, more preferably C1-C2; r3 is selected from aryl of C6-C14, preferably C6-C10, more preferably C6-C8, ester group of C1-C10, preferably C1-C8, more preferably C1-C4, cyano, halogen, pyridine, pyrrolidone, carbazole, amide and alkenyl of C2-C10, preferably C2-C8, more preferably C2-C5, unsubstituted or substituted by halogen.

Further, the vinyl carboxylate copolymer is a random copolymer or a block copolymer, preferably a random copolymer;

the random copolymer is a binary random copolymer, a ternary random copolymer or a random copolymer with more than three elements;

the block copolymer is a diblock copolymer, a triblock copolymer or a multiblock copolymer of more than three blocks, wherein at least one block contains vinyl carboxylate monomer units, preferably the vinyl carboxylate monomer units are randomly distributed in at least one block containing vinyl carboxylate monomer units.

Further, the vinyl carboxylate copolymer is a vinyl acetate copolymer, and the structural formula of the vinyl carboxylate copolymer is shown as a formula IV:

wherein x, m and n represent the degree of polymerization of the same repeating unit; m, n and x are integers between 0 and 100000, preferably 0 to 50000, more preferably 0 to 10000, most preferably 0 to 1000, but x is not zero, preferably x and n are not zero; and m is greater than or equal to x; x + n is greater than 10, preferably greater than 50, preferably greater than 100; x (m-x) is greater than 20:80, preferably greater than 30:70, more preferably greater than 40:60, most preferably greater than 50: 50; wherein x, m and independently of each other may be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 960, 930, 940, 950, 960, 1000, 980, 990, 2000, 3000, 990, 6000, 8000, 90000, 50000, 20000, 50000.

In formula IV, R2 and R3 are as defined above for R2 and R3 in formula II.

Further, the vinyl carboxylate copolymer is

a) A random copolymer selected from the following structural formulae:

wherein x, m and n are as defined above for formula IV;

r4 is H or alkyl of C1-C10, preferably C1-C8, more preferably C1-C4; r5, R6, R7, R8 and R9 are independently selected from H, alkyl of C1-C10, preferably C1-C8, more preferably C1-C4, halogen, alkoxy of C1-C10, preferably C1-C8, more preferably C1-C4, nitro and cyano; (ii) a R10 is H, C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl or C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl; r11 and R12 are independently selected from H and C1-C10, preferably C1-C8, more preferably C1-C4 alkyl; r13 is H, alkyl of C1-C10, preferably C1-C8, more preferably C1-C4 and halogen; r14, R15 and R16 are independently selected from H and alkyl of C1-C10, preferably C1-C8, more preferably C1-C4; r17, R18, R19 and R20 are independently selected from H, C1-C10, preferably C1-C8, more preferably C1-C4 alkyl and halogen; r21, R22, R23 and R24 are independently selected from H, C1-C10, preferably C1-C8, more preferably C1-C4 alkyl and halogen;

or

b) A diblock copolymer or triblock copolymer selected from the following structures,

wherein x, x ', m ', n and n ' represent the degree of polymerization of the respective repeating units; x, x ', m ', n and n ' are integers of 0-100000, preferably 0-50000, more preferably 0-10000, and most preferably 0-1000; but at least one of x and x 'is not zero, preferably at least one of x and x' and n are not zero; and m is greater than or equal to x, m 'is greater than or equal to x'; x or the sum of x' and n is greater than 10, preferably greater than 50, more preferably greater than 100; x (m-x) or x ': m ' -x ') is greater than 20:80, preferably greater than 30:70, more preferably greater than 40:60, most preferably greater than 50: 50; wherein x, x ', m ', n and n ' independently of each other may be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 930, 980, 990, 1000, 2000, 6000, 4000, 70000, 7000, 50000, 7000, 3000, 50000, 7000, 20000, 50000, 7000, 3000, 50000, 7000, 3000, 50000, 7000, 50000, 7000, 3000, 7000, 3000, 50000, 7000, 3000, 700, 950, 850, 1000, 700, 1000, 700, 2000, 700, 840, 180, 700, 180, 700, 180, 700, 180, 700, 180, 700, 180, 700, 500, 90000. 100000; r represents that two adjacent monomer units are randomly distributed in the chain segment; b represents that the structural units in the left and right brackets are connected in a block manner;

wherein R2 and R2' are the same or different and are independently selected from H or alkyl of C1-C10, preferably C1-C8, more preferably C1-C4; r3 and R3' are the same or different and are independently selected from the group consisting of aryl of C6-C14, preferably C6-C10, more preferably C6-C8, ester group of C1-C10, preferably C1-C8, more preferably C1-C4, cyano, halogen, pyridine, pyrrolidone, carbazole, amide and alkenyl of C2-C10, preferably C2-C8, more preferably C2-C4.

The invention also provides a preparation method of the carboxylic acid vinyl ester copolymer, which comprises the following steps:

under the combined action of an oxidant and an additive, polyvinyl ketone or a copolymer thereof reacts to obtain a vinyl carboxylate copolymer;

the additive is at least one of amide compounds, urea compounds, thiourea compounds, ammonium carbamate compounds, organic phosphoric acid compounds, silica reagents, organic phosphorus amide compounds and inorganic salts;

the radical polymerization activity of the comonomer in the vinyl ketone copolymer is higher than that of vinyl carboxylate, and preferably, the ratio of the radical polymerization reactivity ratio of the comonomer to vinyl acetate is 1 to 100000, preferably 4 to 50000, more preferably 10 to 20000.

Further, the structural formula of the polyvinyl ketone or the copolymer thereof is shown as I:

in the formula I, a and n represent the polymerization degree of the corresponding repeating unit, and are integers between 0 and 100000, preferably 0 to 50000, more preferably 0 to 10000, and most preferably 0 to 1000, but a is not zero; and a + n is greater than 10, preferably greater than 50, more preferably greater than 100; wherein a and n, independently of each other, may be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 960, 940, 950, 970, 980, 1000, 980, 990, 2000, 3000, 990, 6000, 8000, 7000, 90000, 7000, 50000, 7000, 50000, 2000000, 50000.

R1 is selected from the group consisting of C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C3-C10, preferably C3-C8, more preferably C3-C5 cycloalkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl; r2 is alkyl of H, F, Cl or C1-C10, preferably C1-C5, more preferably C1-C2; r3 is selected from aryl of C6-C14, preferably C6-C10, more preferably C6-C8, ester group of C1-C10, preferably C1-C8, more preferably C1-C4, cyano, halogen, pyridine, pyrrolidone, carbazole, amide, alkenyl of C2-C10, preferably C2-C8, more preferably C2-C5, unsubstituted OR substituted by halogen, and OR, wherein R represents alkyl of C1-C10, preferably C1-C8, more preferably C1-C4 OR acyl of C2-C10, preferably C2-C8, more preferably C2-C4.

Further, the comonomer in the vinyl ketone copolymer is at least one of the following 1) to 10):

1) styrene or styrene substituted with a substituent selected from the group consisting of C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl;

2) (meth) acrylic acid or (meth) acrylic acid substituted with a substituent selected from the group consisting of C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl; (meth) acrylates or (meth) acrylates substituted by substituents selected from the group consisting of C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl;

3) (meth) acrylamide-based compounds;

4) acrylonitrile or methacrylonitrile;

5) n-vinylcarbazole;

6) n-vinyl pyrrolidone;

7) vinyl chloride or vinylidene chloride;

8) a conjugated diene or a conjugated diene substituted with an alkyl group having from C1 to C10, preferably from C1 to C8, more preferably from C1 to C4;

9) 4-vinylpyridine;

10) 2-vinylpyridine.

Further, the vinyl ketone copolymer is a random copolymer or a block copolymer;

the block copolymer is a diblock copolymer, a triblock copolymer or a multiblock copolymer with more than three blocks, wherein at least one block contains a vinyl ketone monomer unit.

Further, the polyvinyl ketone or the copolymer thereof is polymethyl vinyl ketone or a copolymer thereof, and the structural formula of the polyvinyl ketone or the copolymer thereof is shown as a formula III:

wherein m and n represent the degree of polymerization of the same repeating unit; m and n are integers between 0 and 100000, preferably 0 to 50000, more preferably 0 to 10000, most preferably 0 to 1000; wherein m and n independently of each other may be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 960, 940, 950, 970, 980, 1000, 2000, 3000, 990, 5000, 6000, 8000, 90000, 7000, 50000, 60000, 50000;

wherein R2 and R3 are as defined above for R2 and R3 in formula I.

Further, the methyl vinyl ketone copolymer is a binary random copolymer selected from the following structural formulas,

in each formula, m and n represent the degree of polymerization of the same repeating unit; m and n are integers between 0 and 100000, preferably 0 to 50000, more preferably 0 to 10000, most preferably 0 to 1000; wherein m and n, independently of each other, can be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 960, 940, 950, 970, 980, 1000, 980, 990, 2000, 3000, 990, 6000, 8000, 90000, 7000, 50000, 2000000, 50000, 7000, 50000.

R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 are as defined above for the corresponding radicals of formulae IV-1 to IV-10.

In the preparation method of the invention, the additives are selected as follows:

1) the amide compound is a compound shown as a formula a or a formula b:

in the formula a, R25 is an alkyl group of C1-C10, preferably C1-C8, more preferably C1-C4, an aryl group of C6-C14, preferably C6-C10, more preferably C6-C8, an aralkyl group of C6-C14, preferably C6-C10, more preferably C6-C8 or-CF₃(ii) a R26, R27 and R28 are independently selected from H, C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl;

in the formula b, n is an integer between 1 and 6, preferably 1 to 3;

2) the urea compound is a compound with a structural formula shown as a formula c or a formula d:

in the formula C, R29, R30, R31, R32, R33 and R34 are independently selected from H, C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl;

in the formula d, n is an integer between 1 and 6, preferably 1 to 3;

3) the thiourea compound is a compound with a structural formula shown as a formula e or a formula f:

in the formula e, R35, R36, R37, R38, R39 and R40 are independently selected from H, C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl;

in the formula f, n is an integer between 1 and 6, preferably 1 to 3;

preferably N-methylurea or urea;

4) the carbamate compound is a compound with a structural formula shown as a formula g or a formula h:

in the formula g, R41 and R42 are independently selected from H, C1-C10, preferably C1-C8, more preferably C1-C4 alkyl, C6-C14, preferably C6-C10, more preferably C6-C8 aryl and C6-C14, preferably C6-C10, more preferably C6-C8 aralkyl;

in the formula H, R43 is an alkyl group of C1-C10, preferably C1-C8, more preferably C1-C4, an aryl group of C6-C14, preferably C6-C10, more preferably C6-C8, or an aralkyl group of C6-C14, preferably C6-C10, more preferably C6-C8, R44 and R45 are independently selected from H, an alkyl group of C1-C10, preferably C1-C8, more preferably C1-C4, an aryl group of C6-C14, preferably C6-C10, more preferably C6-C8, and an aralkyl group of C6-C14, preferably C6-C10, more preferably C6-C8;

5) the organic phosphoric acid compound is a compound with a structural formula shown as a formula i:

in the formula i, R46, R47 and R48 are independently selected from alkyl groups of C1-C10, preferably C1-C8, more preferably C1-C4, aryl groups of C6-C14, preferably C6-C10, more preferably C6-C8 and aralkyl groups of C6-C14, preferably C6-C10, more preferably C6-C8;

preferably diphenylphosphinic acid, bis (4-chlorophenyl) phosphinic acid or bis (4-tert-butylphenyl) phosphinic acid;

6) the organic phosphorus amide compound is a compound with a structural formula shown as a formula j:

in the formula j, R49, R50, R51 and R52 are independently selected from alkyl groups of C1-C10, preferably C1-C8, more preferably C1-C4, aryl groups of C6-C14, preferably C6-C10, more preferably C6-C8 and aralkyl groups of C6-C14, preferably C6-C10, more preferably C6-C8;

preferably dinaphthylphosphinic acid amide or diphenylphosphinic acid amide;

7) the silica compound is a compound with a structural formula shown as a formula k, a formula l and a formula p:

in the formula k, the formula l and the formula p, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63 and R64 are independently selected from alkyl groups of C1-C10, preferably C1-C8, more preferably C1-C5; r65, R66, R67 and R68 are independently selected from alkyl groups of C1 to C10, preferably C1 to C8, more preferably C1 to C5 and alkoxy groups of C1 to C10, preferably C1 to C8, more preferably C1 to C5, and at least one is an alkoxy group of C1 to C10, preferably C1 to C8, more preferably C1 to C5;

8) the positive ion of the inorganic salt is NH₄ ⁺、Na⁺、K⁺、Mg²⁺、Ca⁺Or Al³⁺The negative ion is SO₄ ^2-、HSO₄ ^-、CO₃ ^2-、HCO₃ ^-、CN^-、NO₃ ^-、OAc^-、Cl^-Br^-、PO₄ ^3-、HPO₄ ^2-Or H₂PO₄ ^-。

In the preparation method, the oxidant is a peroxybenzoic acid compound shown in the following formula q, a peroxyalkyl carboxylic acid compound shown in the following formula s, a peroxide shown in the following formula t, magnesium monoperoxyphthalate hexahydrate or a urea hydrogen peroxide compound;

in formula q, R69, R70, and R71 are independently selected from H, Cl and nitro; in the formula s, R72 is alkyl or trifluoromethyl of C1-C10, preferably C1-C8, more preferably C1-C5; in the formula t, R73 and R74 are independently selected from H, alkanoyl of C1-C10, preferably C1-C8, more preferably C1-C5, aroyl of C6-C14, preferably C6-C10, more preferably C6-C8.

The preparation method of the invention meets at least one of the following conditions:

a) the solvent for the reaction is halogenated benzene or a mixed solvent of halogenated benzene and saturated aliphatic hydrocarbon of C5-C12, preferably C6-C9;

the halogenated benzene is preferably fluorobenzene, chlorobenzene, o-dichlorobenzene or 1,2, 4-trichlorobenzene;

the saturated aliphatic hydrocarbon is preferably n-hexane, cyclohexane or n-heptane;

b) the reaction temperature is-20-70 ℃, preferably 30-60 ℃, and the reaction time is 0.1-108 hours, preferably 24-42 hours;

c) the molar ratio of the vinyl ketone group in the polymethyl vinyl ketone or the copolymer thereof, the oxidant and the additive is 1: 1-20: 0.001 to 10.

In the preparation method of the invention, the purification can be carried out in the following way: quenching sodium thiosulfate, washing with weak base salt, extracting with an organic solvent, concentrating, and settling; the purification can be carried out by dialysis even in the case of a small amount of reaction.

The invention obtains the copolymer of the polyvinyl carboxylate by oxidizing polyvinyl ketone or the copolymer thereof under specific conditions. Thus, in the process of the present invention, a polyvinyl carboxylate copolymer is obtained by first carrying out radical polymerization using polyvinyl ketone as a monomer and then at least partially oxidizing the ketone group in the resulting polyvinyl ketone or a copolymer thereof to a carboxylate group by oxidation under specific conditions. Therefore, the distribution of the vinyl carboxylate monomer and the comonomer in the polyvinyl carboxylate copolymer is determined by the reactivity ratio of the vinyl ketone monomer and the comonomer, but not by the reactivity ratio of the vinyl carboxylate monomer and the comonomer, so that the problem that the polyvinyl acetate copolymer cannot be obtained by free radical polymerization due to large difference of the reactivity ratios of the vinyl acetate and the high-activity comonomer is solved.

The respective reactivity ratios of vinyl acetate and methyl vinyl ketone with a portion of the comonomers are shown in table 1 below:

TABLE 1 reactivity ratios for vinyl acetate, methyl vinyl ketone and comonomer copolymerization

Therefore, the present invention can very conveniently prepare various copolymers of ethyl carboxylate by using vinyl ketone as a polymerization monomer, and can easily control the content and distribution of vinyl carboxylate monomer units.

Typical reaction example (one) of the present invention: the method comprises the following steps of taking m-chloroperoxybenzoic acid as an oxidant and trichlorobenzene as a reaction solvent, taking polymethyl vinyl ketone as a raw material under the action of an additive, and obtaining a polyvinyl acetate copolymer at a certain temperature, wherein typical reactions are shown in a table 2:

TABLE 2 Oxidation of different molecular weight polymethylketene with different additives

Wherein, the conversion rate refers to the ratio of the number of structural units oxidized into vinyl acetate in the polymer to the number of methyl ketene structural units in the starting raw material, and is obtained by quantitative analysis of nuclear magnetic hydrogen spectrum or carbon spectrum.

Typical reaction example (ii) of the present invention: using other peroxides as an oxidant, and halobenzene or a mixed solvent as a reaction solvent, and using polymethyl vinyl ketone as a raw material under the action of an additive to obtain a polyvinyl acetate copolymer at a certain temperature, wherein a typical reaction is as shown in table 3:

TABLE 3 Oxidation of polymethylvinyl ketones in different oxidants and solvents

Typical reaction example (iii) of the present invention: other types of vinyl ketone homopolymers use m-chloroperoxybenzoic acid as an oxidant and trichlorobenzene as a reaction solvent, and a vinyl carboxylate copolymer is obtained at a certain temperature under the action of an additive, wherein a typical reaction is shown in table 4:

TABLE 4 Oxidation of other types of vinyl ketone homopolymers in m-chloroperoxybenzoic acid in trichlorobenzene solvent

Wherein, the conversion rate refers to the ratio of the number of structural units oxidized into vinyl carboxylate in the polymer to the number of vinyl ketone structural units in the starting material, and is obtained by quantitative analysis of nuclear magnetic hydrogen spectrum or carbon spectrum.

Typical reaction example (iv) of the present invention: taking m-chloroperoxybenzoic acid as an oxidant, trichlorobenzene as a reaction solvent, and taking a random copolymer of methyl vinyl ketone and other high-activity monomers as a raw material under the action of an additive, obtaining a vinyl acetate random copolymer at a certain temperature, wherein a typical reaction is shown in a table 5:

TABLE 5 reaction conversion of random methyl ketene copolymer to random vinyl acetate copolymer

Typical reaction example (v) of the present invention: taking m-chloroperoxybenzoic acid as an oxidant, trichlorobenzene as a reaction solvent, and taking a block copolymer of methyl vinyl ketone and other monomers as a raw material under the action of an additive, obtaining a vinyl acetate block copolymer at a certain temperature, wherein typical reaction examples are shown in Table 6:

TABLE 6 reaction conversion of methyl vinyl ketone Block copolymers to vinyl acetate Block copolymers

From the above results, it can be seen that in the process of the present invention, the conversion rate is controllable and there is no significant cleavage effect on the molecular chain of the polymethylvinylketone or its copolymer as a raw material. I.e. the structural integrity of the molecular chains of the polymer is well maintained. That is, the process of the present invention is capable of controllably converting vinyl ketone monomer units in polyvinyl ketones or copolymers thereof to vinyl carboxylate monomer units, and the structural integrity of the polymer chain itself is well maintained.

The method of the invention conveniently and simply realizes the copolymerization of the carboxylic acid vinyl ester monomer and other high-activity monomers (including styrenes, methacrylates, acrylates, acrylonitrile, acrylamides and the like), avoids the problem of great difference of reactivity ratios between the carboxylic acid vinyl ester monomer and the high-activity monomers, and can obtain random copolymers of the carboxylic acid vinyl ester and other high-activity monomers in any proportion. In addition, since the vinyl ketone monomer has high reactivity and can easily form a block copolymer having an arbitrary structure with other comonomers, the method of the present invention can also obtain a block copolymer of a vinyl carboxylate having an arbitrary structure. Traditional free radical polymerization and even living radical polymerization cannot effectively synthesize block polymers of polyvinyl carboxylate chain segments. The precursor polyvinyl ketone adopted by the preparation method of the invention is an ultraviolet light degradation polymer. In the modification process of the preparation method, the proportion of methyl vinyl ketone structural units in the polyvinyl acetate copolymer can be adjusted by controlling the reaction conversion rate, so that the polyvinyl carboxylate copolymer can also have adjustable photodegradation performance by retaining the polyvinyl ketone structural units. The technology has positive promoting effect in the application field of photodegradation of the polyvinyl carboxylate and even the polyvinyl alcohol copolymer.

The invention also provides a latex containing the vinyl carboxylate copolymer, such as a polyvinyl acetate copolymer. The polyvinyl acetate copolymer latex of the invention not only has the advantages of environmental friendliness, convenient production, high bonding strength, excellent mechanical stability, microbial corrosion resistance, certain oxidation resistance, ultraviolet radiation resistance and the like of the traditional polyvinyl acetate latex, but also has excellent water resistance, heat resistance and mechanical stability; the bonding strength is not significantly reduced even under damp and hot conditions; the rubber has good creep resistance, and the rubber is not easy to slide under the action of long-term load or high temperature; excellent latex stability, and the like.

The invention also provides an adhesive or a coating containing the latex.

Detailed Description

Definition of

The term "(meth) acrylic acid" as used herein means acrylic acid or methacrylic acid.

The abbreviation "St" as used herein means styrene, "MVK" means methyl vinyl ketone, "MMA" means methyl methacrylate, and "MA" means methyl acrylate.

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.

Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.

The starting polymethylvinyl ketone A1-A7 used in examples 1-7 was obtained by "living"/controlled radical polymerization reactions disclosed in the prior art (e.g., J.Am.chem.Soc.,2007,129,10086-10087, to C.Cheng et al). The parameters are shown in Table 2.

The starting material, polymethylvinylketone A8, used in example 8 was prepared by ordinary radical polymerization, the initiator was azobisisobutyronitrile, and the polymerization solvent was ethyl acetate. The parameters are shown in Table 2.

The starting material, polymethylvinylketone A9, used in example 9 is commercially available, e.g., from Sigma-Aldrich. The parameters are shown in Table 2.

The starting material, polymethylvinylketone A10-14, used in examples 10-14 is commercially available, for example, from Sigma-Aldrich. See table 3 (supra) for its parameters.

The starting materials A15-A18 used in examples 15-18 were obtained by the "living"/controlled radical polymerization reaction described above. The parameters are shown in Table 4.

The starting materials A19-A22, A24-A25 and A29-A30 used in examples 19-22, 24-25 and 29-30 were obtained by the "living"/controlled radical polymerization reaction described above. The parameters are shown in Table 5.

The starting materials A23, A26-A28 used in examples 23 and 26 to 28 were prepared by ordinary radical polymerization using azobisisobutyronitrile as an initiator and ethyl acetate as a polymerization solvent. The parameters are shown in Table 5.

The starting materials A31-A36 used in examples 31-36 were obtained by the "living"/controlled radical polymerization reaction described above. The parameters are shown in Table 6.

The present invention will be further explained with reference to examples, but the present invention is not limited to these specific examples, and may be arbitrarily changed without departing from the spirit and scope of the invention.

EXAMPLE 1 Synthesis of vinyl acetate-methylvinyl Ketone copolymer B1 with Diphenylphosphinic acid and dinaphthylphosphine

Under air or nitrogen atmosphere, raw material polymethylvinylketone A1(1g), oxidant m-chloroperoxybenzoic acid (4 equivalents of the mole number of the polymer monomer), additive diphenylphosphinic acid (0.2 equivalent of the mole number of the polymer monomer), additive dinaphthylphosphine amide (equivalent to diphenylphosphinic acid), and solvent trichlorobenzene (2mL) were successively added into the reaction tube. After stirring at room temperature for 10 minutes, the mixture was left at 30 ℃ for reaction for 8 hours. And (3) dialyzing by using ethyl acetate after the reaction is finished, replacing 4-8 times of dialyzate within 1-2 days, vacuumizing to obtain colorless transparent viscous solid, performing sedimentation treatment by using hexane, and grinding after vacuum drying to obtain white powder or granular solid, wherein the monomer conversion rate is 30-40%, and the separation yield is more than 90%.

GPC (THF mobile phase, polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 208 to 213, x is about 62 to 86, and n is 0.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,1H,AcO-CH),2.7-2.3(br s,1H,Ac-CH),2.3-1.92(m,3H,CH₃),1.92-1.5(m,2H,CH₂).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),170.34(s,O-C＝O),67.93-66.02(m,AcO-C),47.94(s,Ac-C),40.14-32.88(m,CH₂),29.92(s,CCO-CH₃)，20.93(s,OCO-CH₃)。

Example 2 Synthesis of vinyl acetate-methyl vinyl Ketone copolymer B2 under the action of Diphenylphosphinic acid and Dinaphthylphosphoramide

The synthesis method is the same as that of the vinyl acetate-methyl vinyl ketone copolymer B1 except that the raw material of the polymethyl vinyl ketone A2(200mg) is reacted for 24 hours.

The monomer conversion rate is 70-80%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 208 to 213, x is about 145 to 171, and n is 0.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,1H,AcO-CH),2.7-2.3(br s,Ac-CH),2.3-1.92(m,3H,CH₃),1.92-1.5(m,2H,CH₂).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),170.34(s,O-C＝O),67.93-66.02(m,AcO-C),47.94(s,Ac-C),40.14-32.88(m,CH₂),29.92(s,CCO-CH₃)，20.93(s,OCO-CH₃)。

Example 3 Synthesis of vinyl acetate-methyl vinyl Ketone copolymer B3 under the action of Diphenylphosphinic acid and dinaphthylphosphine

The synthesis method is the same as that of the vinyl acetate-methyl vinyl ketone copolymer B1 except that the raw material of the polymethyl vinyl ketone A2(200mg) is reacted for 70 hours.

The monomer conversion rate is more than 96 percent, and the separation yield is more than 90 percent.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 208 to 213, x is about 193 to 207, and n is 0.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,1H,AcO-CH),2.7-2.3(br s,Ac-CH),2.3-1.92(m,3H,CH₃),1.92-1.5(m,2H,CH₂).¹³C NMR(101MHz,CDCl₃):δ170.34(s,C＝O),67.93-66.02(m,AcO-C),40.14-38.49(m,CH₂),20.93(s,CH₃)。

EXAMPLE 4 Synthesis of vinyl acetate-methylvinyl ketone copolymer B4 under the action of bis (4-chlorophenyl) phosphinic acid and dinaphthylphosphinic amide

The synthesis method was similar to that of polyvinyl acetate copolymer B3, except that the starting material was polymethylvinylketone A4(200mg), the additive was bis (4-chlorophenyl) phosphinic acid (0.2 equivalent of the molar number of the polymer monomer), and the additive was dinaphthylphosphine phosphinate (equivalent to bis (4-chlorophenyl) phosphinic acid).

The monomer conversion rate is more than 97%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 208 to 213, x is about 190 to 207, and n is 0.

EXAMPLE 5 Synthesis of polyvinyl acetate homopolymer B5 from bis (4-tert-butylphenyl) phosphinic acid and diphenylphosphinic acid amide

The synthesis method is the same as the synthesis of polyvinyl acetate copolymer B1, except that the raw material of the polyvinyl ketone A5(200mg), additive of bis (4-tert-butylphenyl) phosphinic acid (0.2 equivalent of the mole number of the polymer monomer), additive of diphenylphosphine amide (equivalent of bis (4-tert-butylphenyl) phosphinic acid and the like), reaction temperature is 45 ℃ and reaction time is 42 h.

The monomer conversion rate is more than 99 percent, and the separation yield is more than 95 percent.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 222 to 227, x is about 200 to 222, and n is 0.

Example 6 Synthesis of polyvinyl acetate copolymer B6 under the action of Diphenylphosphinic acid amide and Urea

The synthesis method was the same as that for the synthesis of polyvinyl acetate copolymer B5, except that the starting material was polymethylvinylketone A6(200mg), the additive was diphenylphosphinic amide (0.1 equivalent of the molar amount of the polymer monomer), and the additive was urea (equivalent to diphenylphosphinic amide).

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 222 to 227, x is about 200 to 220, and n is 0.

Example 7 Synthesis of polyvinyl acetate copolymer B7 under the action of N-methyl Urea

The synthesis method is the same as that of the polyvinyl acetate copolymer B5 except that the raw material of the polymethyl vinyl ketone A7(200mg) and the additive of N-methyl urea (0.2 equivalent of the mole number of the polymer monomer) are added.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 218 to 223, x is about 200 to 217, and n is 0.

Example 8 Synthesis of polyvinyl acetate copolymer B8 under the action of Urea and sodium sulfate

The synthesis method is the same as that of the polyvinyl acetate copolymer B1, except that the raw material of the polyvinyl ketone A8(200mg), the additive of urea (0.2 equivalent of the mole number of the polymer monomer), and sodium sulfate (0.5g) are added, the reaction temperature is 45 ℃, and the reaction time is 24 hours.

The monomer conversion rate is more than 98 percent, and the separation yield is more than 90 percent.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, the structural formula is shown in formula IV, wherein m is 569-579, x is about 460-569, and n is 0.

Example 9 Synthesis of polyvinyl acetate copolymer B9 by Hexamethylcyclotrisiloxane

Except for the raw material of polymethyl vinyl ketone A9(2g), additive of hexamethylcyclotrisiloxane (2 equivalent of the mole number of polymer monomers), the reaction temperature of 50 ℃ and the reaction time of 24 hours, the synthesis method is the same as the synthesis of polyvinyl acetate copolymer B1.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 2, and the structural formula is shown in formula IV, wherein m is 914-934, x is about 800-910, and n is 0.

Example 10 Synthesis of polyvinyl acetate-methyl vinyl Ketone copolymer B10 under the action of Peroxyacetic acid

Under an air or nitrogen atmosphere, the starting polymethyl vinyl ketone A10(41.7mg), peroxyacetic acid (4 equivalents based on the number of moles of the polymer monomer), an additive (same as in example 1), and trichlorobenzene (2mL) as a solvent were successively added to a reaction tube. Stirring at room temperature for 10min, and reacting at 45 deg.C for 8 h. And (3) dialyzing after the reaction is finished, replacing 4-8 times of dialyzate in 1-2 days, performing vacuum pumping to obtain a colorless transparent viscous solid, performing sedimentation treatment by using hexane, and grinding after vacuum drying to obtain white powder or granular solid, wherein the monomer conversion rate is 5-10%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the number average molecular weight was 70.8kDa, and the PDI was 2.37. + -. 0.3. The structural formula is shown in formula IV, wherein m is 914-934, x is about 45-94, and n is 0.

EXAMPLE 11 Synthesis of polyvinyl acetate-methyl vinyl Ketone copolymer B11 under the action of magnesium monoperoxyphthalate hexahydrate

The synthesis method is the same as that of the polyvinyl acetate copolymer B10, except that the raw material of the polymethyl vinyl ketone A11(41.7mg) and the oxidant of magnesium monoperoxyphthalate hexahydrate (4 equivalents of the mole number of the polymer monomer) are added.

The monomer conversion rate is 10-20%, and the separation yield is more than 80%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the number average molecular weight was 70.8kDa, and the PDI was 2.37. + -. 0.3. The structural formula is shown in formula IV, wherein m is 914-934, x is about 91-187, and n is 0.

EXAMPLE 12 Synthesis of vinyl acetate-methyl vinyl Ketone copolymer B12 with Urea Hydrogen peroxide Complex

The synthesis method is the same as that of polyvinyl acetate copolymer B10 except that the raw material of the polyvinyl ketone A12(41.7mg) and the oxidant of urea-hydrogen peroxide complex (4 equivalents of the mole number of the polymer monomer) are added.

The monomer conversion rate is 5-10%, and the separation yield is more than 80%.

Example 13 Synthesis of vinyl acetate-methyl vinyl Ketone copolymer B13 in Mixed solvent

The synthesis method is the same as that of the polyvinyl acetate copolymer B10 except that the raw material of the polyvinyl ketone A13(41.7mg), the oxidant of m-chloroperoxybenzoic acid (4 equivalents of the mole number of the polymer monomer) and the reaction temperature are 50 ℃.

The monomer conversion rate is 80-90%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the number average molecular weight was 70.8kDa, and the PDI was 2.37. + -. 0.3. The structural formula is shown in formula IV, wherein m is 914-934, x is about 731-840, and n is 0.

EXAMPLE 14 Synthesis of vinyl acetate-methyl vinyl Ketone copolymer B14 in fluorobenzene solvent

Except that the raw material of polymethylvinyl ketone A14(41.7mg) and the solvent of fluorobenzene, the synthesis method is the same as the synthesis of polyvinyl acetate copolymer B13.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the number average molecular weight was 70.8kDa, and the PDI was 2.37. + -. 0.3. The structural formula is shown in formula IV, wherein m is 914-934, x is about 639-750, and n is 0.

Example 15 Synthesis of vinyl propionate-ethyl acrylate-ethylvinyl ketone random copolymer B15

To a reaction tube were successively added, in an air or nitrogen atmosphere, polyethylene vinyl ketone A15(51.2mg), m-chloroperoxybenzoic acid (4 equivalents based on the number of moles of the polymer monomer), an additive (same as in example 1), and trichlorobenzene (2mL) as a solvent. After stirring at room temperature for 10min, the mixture is placed at 40 ℃ for reaction for 14 h. And (3) dialyzing after the reaction is finished, replacing dialyzate for 4-8 times within 1-2 d, performing vacuum pumping to obtain colorless transparent viscous solid, performing sedimentation treatment by using hexane, and grinding after vacuum drying to obtain white powder or granular solid, wherein the monomer conversion rate is 60-70%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): specific data are shown in table 4. The structural formula is shown in formula II, wherein a is 158-164, b is 81-98, c is 13-17, n is 0, and R1 is ethyl.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.86(br s,COO-CH-),4.13(br s,COO-CH₂-CH₃)3-0.5(m,other-CH,-CH₂ and all-CH₃,).¹³C NMR(101MHz,CDCl₃):δ212.71(s,C-C＝O),173.88(s,O-C＝O),65.13-70.02(m,COO-CH₂-CH₃),60.67(s,COO-CH-),47.14(m,CO-CH-),42.15-32.12(m,-CH-CH₂-CH-and CO-CH₂-CH₃)，27.49(s,OCO-CH₂-CH₃),14.12(s,COO-CH₂-CH₃),8.98(s,OCO-CH₂-CH₃),7.10(s,CO-CH₂-CH₃)。

Example 16 Synthesis of vinyl propionate-ethyl acrylate-ethyl vinyl ketone random copolymer B16 Synthesis method was the same as that for polyvinyl acetate copolymer B15 except that the raw material, polyethylvinyl ketone A16(51.2mg), reaction temperature 50 ℃ and reaction time 68h were used.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): specific data are shown in table 4. The structural formula is shown in formula II, wherein a is 158-164, b is 124-133, c is 20-22, n is 0, and R1 is ethyl.

Example 17 Synthesis of vinyl benzoate-phenyl acrylate-phenyl vinyl ketone random copolymer B17

The synthesis method was the same as that for the polyvinyl acetate copolymer B15, except that the starting material was polyphenylvinylketone A17(51.2 mg).

The monomer conversion rate is more than 25-35%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): specific data are shown in table 4. The structural formula is shown in formula II, wherein a is 65-69, b is 16-21, c is 2-5, n is 0, and R1 is phenyl.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ8.11-6.23(br,C₆H₅-),4.99(br s,COO-CH-),3.33(br s,Ph-CO-CH-),2.52-0.55(m,-CH₂ and Ph-OCO-CH-).¹³C NMR(101MHz,CDCl₃):δ202.24(s,C-C＝O),137.32-122.13(m,C₆H₅-),70.02(m,COO-CH-),42.12-31.22(m,OCO-CH-and CO-CH-)。

Example 18 Synthesis of vinyl benzoate-phenyl acrylate-phenyl vinyl ketone random copolymer B18

The synthesis method was the same as that for the polyvinyl acetate copolymer B16, except that the starting material was polyphenylvinylketone A18(78.6 mg).

The monomer conversion rate is more than 70-80%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): specific data are shown in table 4. The structural formula is shown in formula II, wherein a is 65-69, b is 39-49, c is 6-9, n is 0, and R1 is phenyl.

Example 19 Synthesis of styrene-vinyl acetate random copolymer B19

Under an air or nitrogen atmosphere, a raw material styrene-methylvinyl ketone random copolymer A19(200mg, styrene unit content: 50%), an additive (same as in example 1), and trichlorobenzene (8mL) as a solvent were successively added to a reaction tube. After stirring at room temperature for 10min, the mixture is placed at 40 ℃ for reaction for 14 h. And (3) dialyzing after the reaction is finished, replacing 4-8 times of dialyzate within 1-2 d, performing vacuum pumping to obtain a colorless transparent solid, performing sedimentation treatment by using hexane, and grinding after vacuum drying to obtain white powder or granular solid, wherein the monomer conversion rate is more than 99%, and the separation yield is more than 95%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-1, wherein m is 61-66, x is about 60-65, n is 61-66, and R4-R9 are all H.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ7.52-6.29(m,C₆H₅),4.87-4.05(m,AcO-CH),0.76-2.64(overlapping m,CH₂,CH₃ and Ph-CH).¹³C NMR(101MHz,CDCl₃):δ170.21(s,C＝O),146.31-142.29,129.62-125.07(m,C₆H₅),72.55-68.43(m,AcO-C),46.98-37.5(m,CH₂,Ph-C),20.74(s,CH₃)。

Example 20 Synthesis of styrene-vinyl acetate random copolymer B20

The synthesis method was the same as that of styrene-vinyl acetate-methyl vinyl ketone random copolymer B19, except that the starting material styrene-methyl vinyl ketone random copolymer A20(200mg, styrene content: 20%) was reacted at a reaction temperature of 45 ℃.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-1, wherein m is 117 to 122, x is about 105 to 118, n is 28 to 31, and R4 to R9 are all H.

Example 21 Synthesis of styrene-vinyl acetate-methylvinyl ketone random copolymer B21

The synthesis method was the same as that of styrene-vinyl acetate-methyl vinyl ketone random copolymer B19, except that the starting material styrene-methyl vinyl ketone random copolymer A21(200mg, styrene content: 80%) was reacted at a reaction temperature of 30 ℃.

The monomer conversion rate is 65-75%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-1, wherein m is 25 to 29, x is about 16 to 21, n is 110 to 116, and R4 to R9 are all H.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ7.52-6.29(m,C₆H₅),4.87-4.05(m,AcO-CH),0.76-2.64(overlapping m,CH₂,CH₃ and Ph-CH).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),170.21(s,C＝O),146.31-142.29,129.62-125.07(m,C₆H₅),72.55-68.43(m,AcO-C),46.98-37.5(m,CH₂,Ph-C),20.74(s,CH₃)。

Example 22 Synthesis of styrene-vinyl acetate random copolymer B22

The synthesis method was the same as that of styrene-vinyl acetate-methyl vinyl ketone random copolymer B19, except that the starting material styrene-methyl vinyl ketone random copolymer A22(200mg, styrene content 80%) was reacted at a reaction temperature of 35 ℃.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-1, wherein m is 25 to 29, x is about 23 to 28, n is 110 to 116, and R4 to R9 are all H.

Example 23 Synthesis of Acrylonitrile-vinyl acetate random copolymer B23

The synthesis method was the same as that of styrene-vinyl acetate-methyl vinyl ketone random copolymer B19, except that the raw material acrylonitrile-methyl vinyl ketone random copolymer A23(200mg, 20% acrylonitrile) was reacted at 50 ℃.

The monomer conversion rate is more than 99 percent, and the separation yield is more than 90 percent.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-4, wherein m is 310 to 318, x is about 300 to 312, n is 75 to 80, and R4 is H.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ5.51-4.59(m,AcO-CH),3.46-2.46(m,CN-CH),2.46-0.73(overlapping m,CH₂ and CH₃).¹³C NMR(101MHz,CDCl₃):δ170.91(s,C＝O),120.07(br s,CN),71.8-66.56(m,AcO-C),40.25-31.28(m,CH₂),31.28-23.91(m,CN-CH)21.05(s,CH₃)。

Example 24 Synthesis of Acrylonitrile-vinyl acetate-methylvinyl ketone random copolymer B24

The synthesis method is the same as that of the styrene-vinyl acetate-methyl vinyl ketone random copolymer B19 except that the raw material acrylonitrile-methyl vinyl ketone random copolymer A24(200mg, 20 percent of acrylonitrile), the reaction temperature is 45 ℃ and the reaction time is 24 hours.

The monomer conversion rate is 75-85%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-4, wherein m is 68-72, x is about 51-61, n is 68-72, and R4 is H.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ5.51-4.59(m,AcO-CH),3.46-2.46(m,CN-CH),2.46-0.73(overlapping m,CH₂ and CH₃).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),170.91(s,C＝O),120.07(br s,CN),71.8-66.56(m,AcO-C),40.25-31.28(m,CH₂),31.28-23.91(m,CN-CH)21.05(s,CH₃)。

Example 25 Synthesis of methyl methacrylate-vinyl acetate random copolymer B25

The synthesis method is the same as that of the styrene-vinyl acetate-methyl vinyl ketone random copolymer B19 except that the raw material methyl methacrylate-methyl vinyl ketone random copolymer A25(200mg, methyl methacrylate accounts for 20%), the reaction temperature is 50 ℃ and the reaction time is 72 h.

The monomer conversion rate is more than 98 percent, and the separation yield is more than 95 percent.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-2, wherein m is 140 to 145, x is about 130 to 141, n is 33 to 37, and R4 and R10 are both methyl.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,AcO-CH),3.65(br s,COOCH₃),2.28-1.30,1.22-0.77(overlapping m,OCOCH₃ and CH₂).¹³C NMR(101MHz,CDCl₃):δ176.44(br s,C＝OO),170.33(s,OC＝O),69.04-65.65(m,AcO-C),51.78(s,COOCH₃)46.16-37.89(m,CH₂),21.11(s,CH₃)。

Example 26 Synthesis of methyl methacrylate-vinyl acetate-methylvinyl ketone random copolymer B26

The synthesis method was the same as that of the styrene-vinyl acetate-methyl vinyl ketone random copolymer B19, except that the starting material methyl methacrylate-methyl vinyl ketone random copolymer A26(200mg, methyl methacrylate content: 50%) was reacted at a reaction temperature of 50 ℃.

The monomer conversion rate is 60-70%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in Table 5, and the structural formula is shown in formula IV-2, wherein m is 330-346, x is about 196-242, n is 330-346, and R4 and R10 are both methyl.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,AcO-CH),3.65(br s,COOCH₃),2.28-1.30,1.22-0.77(overlapping m,OCOCH₃ and CH₂).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),176.44(br s,C＝OO),170.33(s,OC＝O),69.04-65.65(m,AcO-C),51.78(s,COOCH₃)46.16-37.89(m,CH₂),21.11(s,CH₃)。

Example 27 Synthesis of methyl acrylate-vinyl acetate random copolymer B27

The synthesis method is the same as that of the styrene-vinyl acetate-methyl vinyl ketone random copolymer B19 except that the raw material methyl acrylate-methyl vinyl ketone random copolymer A27(200mg, methyl acrylate accounts for 20%), the reaction temperature is 45 ℃ and the reaction time is 24 hours.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-2, wherein m is 556-566, x is about 520-557, n is 135-142, R4 is H, and R10 is methyl.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,AcO-CH),3.66(br s,COOCH₃),2.61-2.26(m,OCOCH),2.22-1.95(m,OCOCH₃)1.95-1.43(m,CH₂).¹³C NMR(101MHz,CDCl₃):δ170.43(s,C＝O),70.64-65.25(m,AcO-C),51.79(s,COOCH₃)40.82-35.65(overlapping m,CH₂ and CH₃OCOC),20.92(s,CH₃)。

Example 28 Synthesis of methyl acrylate-vinyl acetate-methyl vinyl ketone random copolymer B28 Synthesis was carried out in the same manner as in the synthesis of styrene-vinyl acetate-methyl vinyl ketone random copolymer B19 except that the starting material methyl acrylate-methyl vinyl ketone random copolymer A28(200mg, methyl acrylate content: 20%), the reaction temperature was 45 ℃ and the reaction time was 8 hours.

The monomer conversion rate is 75-85%, and the separation yield is more than 95%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-2, wherein m is 556-566, x is 415-481, n is 135-142, R4 is H, and R10 is methyl.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,AcO-CH),3.66(br s,COOCH₃),2.61-2.26(m,OCOCH),2.22-1.95(m,OCOCH₃)1.95-1.43(m,CH₂).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),170.43(s,C＝O),70.64-65.25(m,AcO-C),51.79(s,COOCH₃)40.82-35.65(overlapping m,CH₂ and CH₃OCOC),20.92(s,CH₃)。

Example 29 Synthesis of N, N-dimethylacrylamide-vinyl acetate-methylvinyl ketone random copolymer B29

The synthesis method is the same as that of the styrene-vinyl acetate-methyl vinyl ketone random copolymer B19 except that the reaction time is 24h except that the raw material N, N-dimethylacrylamide-methyl vinyl ketone random copolymer A29(200mg, N, N-dimethylacrylamide accounts for 50%).

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-3, wherein m is 117-122, x is about 102-117, n is 28-31, R4 is H, and R11 and R12 are both methyl groups.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.86(br s,AcO-CH),2.94(br s,N(CH₃)₂),2.48-1.33(overlapping m,NCOCH,CH₂ and OCOCH₃).¹³C NMR(101MHz,CDCl₃):δ174.5(C＝ON)170.41(s,OC＝O),72.93-64.89(m,AcO-C),42.42-36.01(overlapping m,N(CH₃)₂,CH₂and NCO-C),21.04(s,CH₃)。

EXAMPLE 30 Synthesis of N, N-dimethylacrylamide-vinyl acetate-methylvinyl ketone random copolymer B30

The synthesis method was the same as that of the styrene-vinyl acetate-methyl vinyl ketone random copolymer B19, except that the starting N, N-dimethylacrylamide-methyl vinyl ketone random copolymer A30(200mg, N, N-dimethylacrylamide content: 50%) was used, and the reaction temperature was 45 ℃.

The monomer conversion rate is 85-90%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 5, and the structural formula is shown in formula IV-3, wherein m is 117-122, x is about 99-110, n is 28-31, R4 is H, and R11 and R12 are both methyl groups.

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.86(br s,AcO-CH),2.94(br s,N(CH₃)₂),2.48-1.33(overlapping m,NCOCH,CH₂ and OCOCH₃).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),174.5(C＝ON)170.41(s,OC＝O),72.93-64.89(m,AcO-C),42.42-36.01(overlapping m,N(CH₃)₂,CH₂ and NCO-C),21.04(s,CH₃)。

Example 31 Synthesis of styrene-vinyl acetate diblock copolymer B31

Under an air or nitrogen atmosphere, a starting material styrene-methylvinyl ketone diblock copolymer A31(200mg, 20% styrene unit), additives (the kind and amount used in example 1), a radical scavenger, 2, 6-di-t-butyl-4-methylphenol (0.3% solvent), and trichlorobenzene (8mL) were successively added to a reaction tube. Stirring at room temperature for 10min, and reacting at 40 deg.C for 36 h. And (3) dialyzing after the reaction is finished, replacing 4-8 times of dialyzate within 1-2 d, performing vacuum pumping to obtain a colorless transparent solid, performing sedimentation treatment by using hexane, and grinding after vacuum drying to obtain white powder or granular solid, wherein the monomer conversion rate is more than 99%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 6, and the structural formula is shown in formula V-1, wherein m is 130 to 135, x is about 115 to 131, n is 21 to 24, R2 is H, and R3 is phenyl.

Example 32 Synthesis of styrene- (vinyl acetate/methyl vinyl ketone) diblock copolymer B32

The synthesis method was the same as that of styrene- (vinyl acetate/methyl vinyl ketone) diblock copolymer B31, except that the starting material styrene-methyl vinyl ketone diblock copolymer A32(200mg, methyl methacrylate content: 61%) was reacted for 12 hours. The monomer conversion rate is 65-75%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in table 6, and the structural formula is shown in formula V-1, wherein m is 130 to 135, x is about 83 to 101, n is 21 to 24, R2 is H, and R3 is phenyl.

Example 33 Synthesis of methyl methacrylate-vinyl acetate diblock copolymer B33

The synthesis method is the same as that of the styrene- (vinyl acetate/methyl vinyl ketone) diblock copolymer B31, except that the raw material of the methyl methacrylate-methyl vinyl ketone diblock copolymer A33(200mg, the methyl methacrylate accounts for 61%), the reaction temperature is 45 ℃ and the reaction time is 24 hours. The monomer conversion rate is more than 99 percent, and the separation yield is more than 95 percent.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in Table 6, and the structural formula is shown as V-1, wherein m is 206-216, x is about 185-208, n is 230-240, R2 is methyl, R3 is-COOCH₃。

Example 34 Synthesis of styrene- (vinyl acetate/methyl vinyl ketone) -methyl acrylate triblock copolymer B34

The synthesis method is the same as that of a styrene- (vinyl acetate/methyl vinyl ketone) diblock copolymer B31 except that the raw material of the styrene-methyl vinyl ketone-methyl acrylate triblock copolymer A34(50mg, 34 percent of styrene and 38 percent of methyl acrylate) is reacted for 26 hours. The monomer conversion rate is more than 97%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in Table 6, and the structural formula is shown in V-2, wherein n is 50-54, n ' is 68-72, m is 58-64, x is 53-63, R2 is H, R2 ' is H, R3 is phenyl, R3 ' is-COOCH₃。

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ7.52-6.29(m,C₆H₅),4.87-4.05(m,AcO-CH),0.76-2.64(overlapping m,CH₂,CH₃,OCOCH and Ph-CH).¹³C NMR(101MHz,CDCl₃):δ170.43(s,C＝O),146.31-142.29,129.62-125.07(m,C₆H₅),70.64-65.25(m,AcO-C),51.79(s,COOCH₃),45.12-35.65(overlapping m,CH₂,Ph-C and CH₃OCOC),20.92(s,CH₃)。

EXAMPLE 35 Synthesis of styrene- (vinyl acetate/methyl vinyl ketone) -methyl acrylate triblock copolymer B35

The synthesis method is the same as that of a styrene- (vinyl acetate/methyl vinyl ketone) diblock copolymer B31 except that the raw material of the styrene-methyl vinyl ketone-methyl acrylate triblock copolymer A35(50mg, 34 percent of styrene and 38 percent of methyl acrylate) is reacted for 26 hours. The monomer conversion rate is 70-80%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in Table 6, and the structural formula is shown in V-2, wherein n is 50-54, n ' is 68-72, m is 58-64, x is 40-51, R2 is H, R2 ' is H, R3 is phenyl, R3 ' is-COOCH₃。

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ7.52-6.29(m,C₆H₅),4.87-4.05(m,AcO-CH),0.76-2.64(overlapping m,CH₂,CH₃,OCOCH and Ph-CH).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),170.43(s,C＝O),146.31-142.29,129.62-125.07(m,C₆H₅),70.64-65.25(m,AcO-C),51.79(s,COOCH₃),45.12-35.65(overlapping m,CH₂,Ph-C and CH₃OCOC),20.92(s,CH₃)。

Example 36 Synthesis of vinyl acetate-methyl acrylate-vinyl acetate triblock copolymer B36

The synthesis method is the same as that of a styrene- (vinyl acetate/methyl vinyl ketone) diblock copolymer B31 except that a raw material of a methyl vinyl ketone-methyl acrylate-methyl vinyl ketone triblock copolymer A36(50mg, the methyl acrylate accounts for 39%), the reaction temperature is 50 ℃, and the reaction time is 14 h. The monomer conversion rate is more than 99 percent, and the separation yield is more than 90 percent.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in Table 6, and the structural formula is shown in V-4, wherein n is 63-67, m is 88-93, m' is 35-39, and x is 82 ℃; E92, x' is 30-39, R2 is H, R3 is-COOCH₃。

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,AcO-CH),3.66(br s,COOCH₃),2.61-2.26(m,OCOCH),2.22-1.95(m,OCOCH₃)1.95-1.43(m,CH₂).¹³C NMR(101MHz,CDCl₃):δ170.43(s,C＝O),70.64-65.25(m,AcO-C),51.79(s,COOCH₃),40.82-35.65(overlapping m,CH₂ and CH₃OCOC),20.92(s,CH₃)。

EXAMPLE 37 Synthesis of methyl (vinyl acetate/methyl vinyl ketone) -acrylic acid methyl ester- (vinyl acetate/methyl vinyl ketone) triblock copolymer B37

The synthesis method is the same as that of a styrene- (vinyl acetate/methyl vinyl ketone) diblock copolymer B31 except that a raw material of a methyl vinyl ketone-methyl acrylate-methyl vinyl ketone triblock copolymer A37(50mg, the methyl acrylate accounts for 39%), the reaction temperature is 40 ℃, and the reaction time is 8 hours. The monomer conversion rate is 50-60%, and the separation yield is more than 90%.

GPC (THF mobile phase, PS calibrnation polystyrene standard calibration): the specific data are shown in Table 6, and the structural formula is shown in V-4, wherein n is 63-67, m is 88-93, m 'is 35-39, x is 43-56, x' is 16-24, R2 is H, R3 is-COOCH₃。

Nuclear magnetic characterization¹H NMR(400MHz,CDCl₃):δ4.85(br s,AcO-CH),3.66(br s,COOCH₃),2.61-2.26(m,OCOCH),2.22-1.95(m,OCOCH₃)1.95-1.43(m,CH₂).¹³C NMR(101MHz,CDCl₃):δ210.17(s,C-C＝O),170.43(s,C＝O),70.64-65.25(m,AcO-C),51.79(s,COOCH₃),40.82-35.65(overlapping m,CH₂ and CH₃OCOC),20.92(s,CH₃)。

As demonstrated in the above examples, without being bound by any theory, the process of the present invention, by using specific additives and oxidants, not only is the reaction rate fast, enabling efficient conversion of vinyl ketone monomer units to vinyl carboxylate monomer units, but also the conversion rate thereof can be controlled, enabling copolymers having specific structures. In addition, the method of the present invention does not cut the chain of the polymer as a raw material, that is, the polymerization degree of the polymer before and after the reaction is substantially unchanged.

Claims

1. A vinyl carboxylate copolymer having a structural formula as shown in formula II:

in the formula, a, b, c and n represent the polymerization degree of corresponding repeating units, and are integers between 0 and 100000, but a and b are not zero, and a is more than b + c; b + n is greater than 10; (b + c) greater than 20: 80;

wherein R1 is selected from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C14 aryl and C6-C14 aralkyl; r2 is H, F, Cl or C1-C10 alkyl; r3 is selected from aryl of C6-C14, ester of C1-C10, cyano, halogen, pyridine, pyrrolidone, carbazole, amide and unsubstituted or halogen-substituted alkenyl of C2-C10;

the preparation method of the vinyl carboxylate copolymer comprises the following steps:

the free radical polymerization activity of a comonomer in the vinyl ketone copolymer is higher than that of vinyl carboxylate, and the ratio of the free radical polymerization reactivity ratio of the comonomer to the vinyl acetate is 1-100000;

the oxidant is a peroxybenzoic acid compound shown in the following formula q, a peroxyalkyl carboxylic acid compound shown in the following formula s, a peroxide shown in the following formula t, magnesium monoperoxyphthalate hexahydrate or a urea hydrogen peroxide compound;

in formula q, R69, R70, and R71 are independently selected from H, Cl and nitro; in the formula s, R72 is C1-C10 alkyl or trifluoromethyl; in the formula t, R73 and R74 are independently selected from H, alkanoyl of C1-C10 and aroyl of C6-C14.

2. The vinyl carboxylate copolymer according to claim 1, wherein a, b, c and n are integers of 0 to 50000, and a, b and n are not zero; b + n is greater than 50; (b + c) greater than 30:70 (a-b-c);

wherein R1 is selected from C1-C8 alkyl, C3-C8 cycloalkyl, C6-C10 aryl and C6-C10 aralkyl; r2 is C1-C5 alkyl; r3 is selected from C6-C10 aryl, C1-C8 ester, and C2-C8 alkenyl which is unsubstituted or substituted by halogen.

3. The vinyl carboxylate copolymer according to claim 1, wherein a, b, c and n are each an integer of 0 to 10000; b + n is greater than 100; (b + c) greater than 40:60 (a-b-c);

wherein R1 is selected from C1-C4 alkyl, C3-C5 cycloalkyl, C6-C8 aryl and C6-C8 aralkyl; r2 is C1-C2 alkyl; r3 is selected from C6-C8 aryl, C1-C4 ester, and C2-C5 alkenyl which is unsubstituted or substituted by halogen.

4. The vinyl carboxylate copolymer according to claim 1, wherein a, b, c and n are each an integer of 0 to 1000; (b + c) and (a-b-c) is greater than 50: 50.

5. The vinyl carboxylate copolymer according to claim 1, wherein the vinyl carboxylate copolymer is a random copolymer or a block copolymer;

the block copolymer is a diblock copolymer, a triblock copolymer or a multiblock copolymer of more than three blocks, wherein at least one block contains a vinyl carboxylate monomer unit.

6. The vinyl carboxylate copolymer according to any one of claims 1 to 5, wherein the vinyl carboxylate copolymer is a vinyl acetate copolymer having a structural formula shown in formula IV:

in each formula, x, m and n represent the degree of polymerization of the corresponding repeating unit; m, n and x are integers between 0 and 100000, but x is not zero; and m is greater than x; x + n is greater than 10; x (m-x) is more than 20: 80;

in the formula IV, R2 and R3 are as defined for R2 and R3 of formula II in claim 1.

7. The vinyl carboxylate copolymer according to claim 6, wherein m, n and x are integers between 0 and 50000, and neither x nor n is zero; x + n is greater than 50; x (m-x) is more than 30: 70.

8. The vinyl carboxylate copolymer according to claim 6, wherein m, n and x are integers between 0 and 10000; x + n is greater than 100; x (m-x) is more than 40: 60.

9. The vinyl carboxylate copolymer according to claim 6, wherein m, n and x are integers from 0 to 1000; x (m-x) is more than 50: 50.

10. The vinyl carboxylate copolymer according to claim 6, wherein the vinyl acetate copolymer is

a) A random copolymer selected from the following structures:

r4 is H or alkyl of C1-C10; r5, R6, R7, R8 and R9 are independently selected from H, C1-C10 alkyl, halogen, C1-C10 alkoxy, nitro and cyano; r10 is H, C1-C10 alkyl, C6-C14 aryl or C6-C14 aralkyl; r11 and R12 are independently selected from H and C1-C10 alkyl; r13 is H, alkyl of C1-C10 and halogen; r14, R15 and R16 are independently selected from H and C1-C10 alkyl; r17, R18, R19, R20, R21, R22, R23 and R24 are independently selected from H, C1-C10 alkyl and halogen;

or

wherein x, x ', m ', n and n ' represent the degree of polymerization of the respective repeating units; x, x ', m ', n and n ' are integers between 0 and 100000; but at least one of x and x' is not zero; and m is greater than x, m 'is greater than x'; x or the sum of x' and n is greater than 10; x (m-x) or x ': m ' -x ') is greater than 20: 80; r represents that two adjacent monomer units are randomly distributed in the chain segment; b represents that the structural units in the left and right brackets are connected in a block manner;

wherein R2 and R2' are the same or different and are independently selected from H or C1-C10 alkyl; r3 and R3' are the same or different and are independently selected from the group consisting of C6-C14 aryl, C1-C10 ester, cyano, halogen, pyridine, pyrrolidone, carbazole, amide and unsubstituted or halogen-substituted C2-C10 alkenyl.

11. The vinyl carboxylate copolymer as claimed in claim 10, wherein the vinyl acetate copolymer is

a) In the formulas, m, n and x are integers between 0 and 50000, and x and n are not zero; x + n is greater than 50; x (m-x) is more than 30: 70;

r4 is C1-C8 alkyl; r5, R6, R7, R8 and R9 are independently selected from C1-C8 alkyl groups, C1-C8 alkoxy groups; r10 is C1-C8 alkyl, C6-C10 aryl or C6-C10 aralkyl; r11 and R12 are independently selected from C1-C8 alkyl; r13 is C1-C8 alkyl; r14, R15 and R16 are independently selected from C1-C8 alkyl; r17, R18, R19, R20, R21, R22, R23, and R24 are independently selected from C1-C8 alkyl;

or

b) Wherein x, x ', m ', n and n ' are integers between 0 and 50000; n and at least one of x and x' are not zero; x or the sum of x' and n is greater than 50; x (m-x) or x ': m ' -x ') is greater than 30: 70;

wherein R2 and R2' are the same or different and are independently selected from C1-C8 alkyl; r3 and R3' are the same or different and are independently selected from the group consisting of C6-C10 aryl, C1-C8 ester, and unsubstituted or halogen-substituted C2-C8 alkenyl.

12. The vinyl carboxylate copolymer as claimed in claim 10, wherein the vinyl acetate copolymer is

a) In the formulas, m, n and x are integers between 0 and 10000; x + n is greater than 100; x (m-x) is more than 40: 60;

r4 is C1-C4 alkyl; r5, R6, R7, R8 and R9 are independently selected from C1-C4 alkyl groups, C1-C4 alkoxy groups; r10 is C1-C4 alkyl, C6-C8 aryl or C6-C8 aralkyl; r11 and R12 are independently selected from C1-C4 alkyl; r13 is C1-C4 alkyl; r14, R15 and R16 are independently selected from C1-C4 alkyl; r17, R18, R19, R20, R21, R22, R23, and R24 are independently selected from C1-C4 alkyl;

or

b) Wherein x, x ', m ', n and n ' are integers between 0 and 10000; x or the sum of x' and n is greater than 100; x (m-x) or x ': m ' -x ') is greater than 40: 60;

wherein R2 and R2' are the same or different and are independently selected from C1-C4 alkyl; r3 and R3' are the same or different and are independently selected from the group consisting of C6-C8 aryl, C1-C4 ester, and unsubstituted or halogen-substituted C2-C4 alkenyl.

13. The vinyl carboxylate copolymer as claimed in claim 10, wherein the vinyl acetate copolymer is

a) In the formulas, m, n and x are integers between 0 and 1000; x (m-x) is more than 50: 50; or

b) Wherein x, x ', m ', n and n ' are integers of 0 to 1000; x (m-x) or x ': m ' -x ') is greater than 50: 50.

14. A process for preparing the vinyl carboxylate copolymer of claim 1, comprising the steps of:

15. The production method according to claim 14, wherein the ratio of the free radical polymerization reactivity ratio of the comonomer to vinyl acetate is 4 to 50000;

in the formula s, R72 is C1-C8 alkyl; in the formula t, R73 and R74 are independently selected from C1-C8 alkanoyl and C6-C10 aroyl.

16. The production method according to claim 14, wherein the ratio of the free radical polymerization reactivity ratio of the comonomer to vinyl acetate is 10 to 20000;

in the formula s, R72 is C1-C5 alkyl; in the formula t, R73 and R74 are independently selected from C1-C5 alkanoyl and C6-C8 aroyl.

17. The method of claim 14, wherein the polyvinyl ketone or copolymer thereof has the structural formula I:

in the formula I, a and n represent the polymerization degree of corresponding repeating units, and are integers between 0 and 100000, but a is not zero; and a + n is greater than 10;

r1 is selected from C1-C10 alkyl, C3-C10 cycloalkyl, C6-C14 aryl and C6-C14 aralkyl; r2 is H, F, Cl or C1-C10 alkyl; r3 is selected from C6-C14 aryl, C1-C10 ester, cyano, halogen, pyridine, pyrrolidone, carbazole, amide, unsubstituted OR halogen-substituted C2-C10 alkenyl, and OR, wherein R represents C1-C10 alkyl OR C2-C10 acyl.

18. The preparation method according to claim 17, wherein in formula I, a and n represent the degree of polymerization of the respective repeating units, each being an integer of 0 to 50000; and a + n is greater than 50;

r1 is selected from C1-C8 alkyl, C3-C8 cycloalkyl, C6-C10 aryl and C6-C10 aralkyl; r2 is C1-C5 alkyl; r3 is selected from C6-C10 aryl, C1-C8 ester, unsubstituted OR halogen-substituted C2-C8 alkenyl, and OR, wherein R represents C1-C8 alkyl OR C2-C8 acyl.

19. The preparation method according to claim 17, wherein in formula I, a and n represent the degree of polymerization of the corresponding repeating unit, and are each an integer of 0 to 10000; and a + n is greater than 100;

r1 is selected from C1-C4 alkyl, C3-C5 cycloalkyl, C6-C8 aryl and C6-C8 aralkyl; r2 is C1-C2 alkyl; r3 is selected from C6-C8 aryl, C1-C4 ester, unsubstituted OR halogen-substituted C2-C5 alkenyl, and OR, wherein R represents C1-C4 alkyl OR C2-C4 acyl.

20. The method according to claim 17, wherein a and n in formula I represent the degree of polymerization of the corresponding repeating unit, and each is an integer of 0 to 1000.

21. The method of claim 14, wherein: the comonomer in the vinyl ketone copolymer is at least one of the following 1) to 10):

1) styrene or styrene substituted with a substituent selected from the group consisting of C1-C10 alkyl, C6-C14 aryl and C6-C14 aralkyl;

2) (meth) acrylic acid or (meth) acrylic acid substituted with a substituent selected from the group consisting of C1-C10 alkyl, C6-C14 aryl and C6-C14 aralkyl; (meth) acrylate or (meth) acrylate substituted with a substituent selected from the group consisting of C1-C10 alkyl, C6-C14 aryl and C6-C14 aralkyl;

3) (meth) acrylamide-based compounds;

4) acrylonitrile or methacrylonitrile;

5) n-vinylcarbazole;

6) n-vinyl pyrrolidone;

7) vinyl chloride or vinylidene chloride;

8) conjugated diene or conjugated diene substituted by C1-C10 alkyl;

9) 4-vinylpyridine;

10) 2-vinylpyridine.

22. The method of manufacturing according to claim 21, wherein:

1) styrene or styrene substituted with a substituent selected from the group consisting of C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

2) (meth) acrylic acid or (meth) acrylic acid substituted with a substituent selected from the group consisting of C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl; (meth) acrylates or (meth) acrylates substituted with substituents selected from the group consisting of C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

8) conjugated diolefins or conjugated diolefins substituted with C1-C8 alkyl groups.

23. The method of manufacturing according to claim 21, wherein:

1) styrene or styrene substituted with a substituent selected from the group consisting of C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

2) (meth) acrylic acid or (meth) acrylic acid substituted with a substituent selected from the group consisting of C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl; (meth) acrylates or (meth) acrylates substituted with substituents selected from the group consisting of C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

8) conjugated diolefins or conjugated diolefins substituted with C1-C4 alkyl groups.

24. The method of claim 14, wherein: the vinyl ketone copolymer is a random copolymer or a block copolymer;

25. The method of claim 17, wherein: the polyvinyl ketone or the copolymer thereof is polymethyl vinyl ketone or a copolymer thereof, and the structural formula of the polyvinyl ketone or the copolymer thereof is shown as a formula III:

wherein m, n, R2 and R3 are as defined in claim 17 for a, n, R2 and R3 of formula I.

26. The method of claim 25, wherein: the methyl vinyl ketone copolymer is a binary random copolymer selected from the following structural formulas,

wherein m and n are as defined in claim 17 for a and n of formula I;

r4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 are as defined in claim 10 for the corresponding groups of formulae IV-1 to IV-10.

27. The method of claim 14, wherein:

the amide compound is a compound shown as a formula a or a formula b:

in the formula a, R25 is C1-C10 alkyl, C6-C14 aryl, C6-C14 aralkyl or-CF₃(ii) a R26, R27 and R28 are independently selected from H, C1-C10 alkyl, C6-C14 aryl and C6-C14 aralkyl;

in the formula b, n is an integer between 1 and 6;

the urea compound is a compound with a structural formula shown as a formula c or a formula d:

in the formula C, R29, R30, R31, R32, R33 and R34 are independently selected from H, alkyl of C1-C10, aryl of C6-C14 and aralkyl of C6-C14;

in the formula d, n is an integer between 1 and 6;

the thiourea compound is a compound with a structural formula shown as a formula e or a formula f:

in the formula e, R35, R36, R37, R38, R39 and R40 are independently selected from H, alkyl of C1-C10, aryl of C6-C14 and aralkyl of C6-C14;

in the formula f, n is an integer between 1 and 6;

the carbamate compound is a compound with a structural formula shown as a formula g or a formula h:

in the formula g, R41 and R42 are independently selected from H, C1-C10 alkyl, C6-C14 aryl and C6-C14 aralkyl;

in the formula H, R43 is C1-C10 alkyl, C6-C14 aryl or C6-C14 aralkyl, R44 and R45 are independently selected from H, C1-C10 alkyl, C6-C14 aryl and C6-C14 aralkyl;

the organic phosphoric acid compound is a compound with a structural formula shown as a formula i:

in the formula i, R46, R47 and R48 are independently selected from C1-C10 alkyl, C6-C14 aryl and C6-C14 aralkyl;

the organic phosphorus amide compound is a compound with a structural formula shown as a formula j:

in the formula j, R49, R50, R51 and R52 are independently selected from alkyl of C1-C10, aryl of C6-C14 and aralkyl of C6-C14;

the silica compound is a compound with a structural formula shown as a formula k, a formula l and a formula p:

in the formula k, the formula l and the formula p, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63 and R64 are independently selected from alkyl of C1-C10; r65, R66, R67 and R68 are independently selected from C1-C10 alkyl and C1-C10 alkoxy, and at least one is C1-C10 alkoxy;

the positive ion of the inorganic salt is NH₄ ⁺、Na⁺、K⁺、Mg²⁺、Ca⁺Or Al³⁺The negative ion is SO₄ ^2-、HSO₄ ^-、CO₃ ^2-、HCO₃ ^-、CN^-、NO₃ ^-、OAc^-、Cl^-、Br^-、PO₄ ^3-、HPO₄ ^2-Or H₂PO₄ ^-。

28. The method of manufacturing according to claim 27, wherein:

in the formula a, R25 is C1-C8 alkyl, C6-C10 aryl, C6-C10 aralkyl; r26, R27 and R28 are independently selected from C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

in the formula b, n is an integer between 1 and 3;

in the formula C, R29, R30, R31, R32, R33 and R34 are independently selected from C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

in the formula d, n is an integer between 1 and 3;

in the formula e, R35, R36, R37, R38, R39 and R40 are independently selected from C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

in the formula f, n is an integer between 1 and 3;

in the formula g, R41 and R42 are independently selected from C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

in the formula h, R43 is C1-C8 alkyl, C6-C10 aryl or C6-C10 aralkyl; r44 and R45 are independently selected from the group consisting of C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

in the formula i, R46, R47 and R48 are independently selected from C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

in the formula j, R49, R50, R51 and R52 are independently selected from C1-C8 alkyl, C6-C10 aryl and C6-C10 aralkyl;

in the formula k, the formula l and the formula p, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63 and R64 are independently selected from alkyl groups of C1-C8; r65, R66, R67 and R68 are independently selected from C1-C8 alkyl and C1-C8 alkoxy, and at least one is C1-C8 alkoxy.

29. The method of manufacturing according to claim 27, wherein:

in the formula a, R25 is C1-C4 alkyl, C6-C8 aryl, C6-C8 aralkyl; r26, R27 and R28 are independently selected from C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

in the formula C, R29, R30, R31, R32, R33 and R34 are independently selected from C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

in the formula e, R35, R36, R37, R38, R39 and R40 are independently selected from C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

in the formula g, R41 and R42 are independently selected from C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

in the formula h, R43 is C1-C4 alkyl, C6-C8 aryl or C6-C8 aralkyl; r44 and R45 are independently selected from the group consisting of C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

in the formula i, R46, R47 and R48 are independently selected from C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

in the formula j, R49, R50, R51 and R52 are independently selected from C1-C4 alkyl, C6-C8 aryl and C6-C8 aralkyl;

in the formula k, the formula l and the formula p, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63 and R64 are independently selected from alkyl groups of C1-C5; r65, R66, R67 and R68 are independently selected from C1-C5 alkyl and C1-C5 alkoxy, and at least one is C1-C5 alkoxy.

30. The production method according to any one of claims 14 to 29, characterized in that: at least one of the following conditions is satisfied:

a) the solvent for the reaction is halogenated benzene or a mixed solvent of halogenated benzene and saturated aliphatic hydrocarbon of C5-C12;

b) the reaction temperature is-20 ℃ to 70 ℃, and the reaction time is 0.1 h to 108 h;

31. The method of claim 30, wherein: at least one of the following conditions is satisfied:

a) the solvent for the reaction is halogenated benzene or a mixed solvent of halogenated benzene and saturated aliphatic hydrocarbon of C6-C9;

the halogenated benzene is fluorobenzene, chlorobenzene, o-dichlorobenzene or 1,2, 4-trichlorobenzene;

the saturated aliphatic hydrocarbon is n-hexane, cyclohexane or n-heptane;

b) the reaction temperature is 30-60 ℃, and the reaction time is 24-42 h.

32. A latex comprising the vinyl carboxylate copolymer of any one of claims 1 to 13.

33. An adhesive or coating comprising the latex of claim 32.