CN105949401B - A kind of acrylic ester grafted modified PET copolymer and its preparation and application - Google Patents

Abstract

The present invention relates to a kind of acrylate graft modified PET copolymer and its preparation and application. After reacting the vinyl monomer of the group to prepare the macromonomer containing the modified PET segment, it is copolymerized with the vinyl monomer; the molecular weight of the acrylate graft modified PET copolymer is 8000 ~ 80000 g/mol; The weight percent content of the macromonomer in the copolymerization reaction is 1-20%. The present invention modifies vinyl polymers such as acrylates by adding macromolecular functional monomers, which can improve the adhesion of coatings and inks on PET surfaces, and can be used as PET coatings and inks to increase the adhesion of coatings and inks on PET surfaces. Greatly improved, not easy to fall off, good durability, improve the surface printing and coating performance of PET substrates. Moreover, the process is simple, the cost is low, and PET does not need surface treatment; it has huge application prospects and market value.

Description

A kind of acrylate graft modified PET copolymer and its preparation and application

technical field

The invention relates to the field of copolymers, in particular to an acrylate graft-modified PET copolymer and its preparation and application.

Background technique

PET (polyethylene terephthalate) is suitable for durable outdoor product labels, packaging and other fields due to its low production cost, high transparency, corrosion resistance, high temperature resistance, chemical properties and dimensional stability. The field requires that PET products must be painted and printed. However, since PET is a non-absorbent printing material, lacks polar groups, has low surface tension, and poor hygroscopicity, coatings or inks cannot be effectively combined with the surface of PET substrates, and the adhesion effect is poor, and it is easy to fall off, affecting product quality and limiting its use. application. Therefore, develop a new type of acrylic or styrene polyethylene terephthalate macromer, and copolymerize it with other acrylic monomers, styrene-based monomers, and vinyl acetate monomers to prepare Acrylate resin with excellent adhesion to PET has important practical significance and application value.

Adhesion is the basis for the protection, decoration and special functions of the coating film and ink. Even if the coating film and ink have excellent physical and chemical properties, if they cannot be firmly bonded to the substrate, they will have no use value. Adhesion promoters can improve the adhesion of coatings and inks to substrates, enabling them to perform functions such as protection and decoration.

At present, in order to ensure the adhesion to the surface of PET products, corona treatment must be carried out on PET before coating or printing. The electric shock treatment method is used to make the PET surface chemically react to generate polar organic groups and increase its surface polarity. Improve the adhesion of coatings and inks. However, corona-treated materials have poor surface tension stability, and the corona effect will gradually weaken over time. Moreover, corona treatment is only suitable for the surface treatment of regular surface items such as films, and corona treatment is powerless for components with complex structures. Adding PET adhesion promoter can improve the adhesion of paint and ink to PET. However, the compatibility of PET adhesion promoters with some coatings and inks is poor, and the addition of adhesion promoters will affect the gloss and other properties of coatings and inks. PET has good adhesion to its substrate. However, ordinary PET can only be dissolved in solvents such as trifluoroacetic acid, pyridine, phenol-tetrachloroethane, etc. These solvents are highly toxic and smelly, so they are not suitable for coatings and inks. Solvent use.

Based on the needs of industry and practical applications, it is necessary to find a PET coating that has a simple synthesis process, can be dissolved in low-toxic, volatile organic solvents such as ethyl acetate and methyl ethyl ketone or in water, and has good adhesion to the PET substrate. Ink to ensure good adhesion of paint and ink to PET substrates.

Contents of the invention

The first purpose of the present invention is to provide a kind of acrylate graft modified PET copolymer, to solve the poor compatibility between PET adhesion promoter and some coatings, printing ink, adding adhesion promotion agent can affect the luster of coating, printing ink etc. performance issues.

In order to achieve the above purpose, the following technical solutions are adopted:

An acrylate graft-modified PET copolymer prepared by reacting modified PET containing terminal hydroxyl or carboxyl groups and vinyl monomers containing groups capable of reacting with terminal hydroxyl groups or containing groups capable of reacting with terminal carboxyl groups After the macromonomer containing the modified PET chain segment, it is copolymerized with vinyl monomer; the molecular weight of the acrylate graft modified PET copolymer is 8000~80000 g/mol; the macromolecular unit in the copolymerization reaction The body weight percentage is 1~20%. PET has better solubility after modification. The modified PET contains terminal hydroxyl or carboxyl groups, which can react with vinyl monomers containing reactive groups to prepare macromonomers.

The addition of the macromonomer can improve the adhesion of the paint and the ink on the surface of the PET polymer, and has little effect on the gloss of the paint and the ink. The molecular structure of the acrylate graft modified PET copolymer contains a modified PET segment of the parent body, which can be anchored on the surface of the PET substrate, providing adhesion to the surface of the substrate, and preparing a copolymer containing the hydrophilic PET segment. It can be used as PET coating and printing ink to obtain good surface adhesion.

Macromonomer content and molecular weight are important indicators that affect the performance of acrylate graft modified PET copolymers. When the macromonomer addition is 1-20%, the acrylate graft modified PET copolymer has a better effect on PET. Adhesion performance, when the amount of macromer added is 5-10%, the acrylate graft modified PET copolymer has the best adhesion effect on PET. When the molecular weight is in the range of 8000-80000 g/mol, the acrylate graft modified PET copolymer has better solubility, adhesion and other comprehensive properties. The comprehensive performance is the best when the molecular weight is 10000~40000 g/mol.

Further, the macromonomers containing modified PET segments are acrylate macromers containing modified PET segments, methacrylate macromers containing modified PET segments, One or more of the styrene-type macromolecular monomers that modify the PET chain segment.

Further, the vinyl monomer containing a group capable of reacting with terminal hydroxyl groups is one of acrylic acid, acryloyl chloride, methacrylic acid, methacryloyl chloride, p-chloromethyl styrene, p-bromomethyl styrene one or more; the vinyl monomers containing groups capable of reacting with terminal carboxyl groups are glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate , one or more of hydroxypropyl methacrylate.

Further, the vinyl monomer is methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, Styrene, vinyl acetate, acrylic acid, glycidyl acrylate, hydroxyethyl acrylate, methacrylic acid, glycidyl methacrylate, hydroxyethyl methacrylate, and sodium styrene sulfonate.

Further, the acrylate graft modified PET copolymer is oil-soluble, and the vinyl monomer contains 0%-5% water-soluble vinyl monomer and 95%-100% oil-soluble vinyl monomer .

Further, the acrylate graft-modified PET copolymer is water-soluble, and the vinyl monomer contains 60%-90% oil-soluble vinyl monomer and 10%-40% water-soluble vinyl monomer .

The macromonomer is a lipophilic functional monomer. When the added comonomer vinyl monomer is water-soluble, the acrylate graft-modified PET copolymer containing macromonomer structural units will have certain water solubility. Or water-dispersible, can be used as water-based PET bottom coating or water-based PET coating, printing ink. When the added comonomer vinyl monomer is oil-soluble or slightly water-soluble, the acrylate graft-modified PET copolymer containing macromonomer structural units will have oil solubility and can be used as an oily PET bottom coating or Used in oily PET coatings and printing inks. However, if the comonomer vinyl monomers are all water-soluble, the water solubility is good, but the water resistance is poor, and the water resistance can be increased by adding oil-soluble monomers appropriately. Adding a proper amount of water-soluble vinyl monomer to oil-soluble comonomer vinyl monomer can increase wettability.

Further, the modified PET containing terminal hydroxyl group or carboxyl group is a modified PET containing terminal hydroxyl group at one end and carboxyl terminal group at the other end. When one end is a terminal hydroxyl group and the other end is a terminal carboxyl group, you can use acetyl chloride, acetic acid, etc. to carry out a capping reaction with the terminal hydroxyl group first, and the other unreacted end, the terminal carboxyl group, reacts with vinyl monomer to form a macromer . When one end is a terminal hydroxyl group and the other end is a terminal carboxyl group, ethanol, methanol, etc. can be used for capping reaction with the terminal carboxyl group, and the unreacted other end, the terminal hydroxyl group, is then reacted with a vinyl monomer to form a macromer.

The second object of the present invention is to provide a preparation method of acrylate graft-modified PET copolymer, provide a kind of synthesis process is simple and convenient, can be dissolved in low toxicity, volatile organic solvent or water, and have good compatibility with PET base material Adhesive acrylate graft modified PET copolymer to ensure good adhesion of coatings and inks to PET substrates.

A kind of preparation method of above-mentioned acrylate graft modified PET copolymer mainly comprises the following steps:

(1) Preparation of modified PET containing terminal hydroxyl or carboxyl groups;

(2) Dissolve the modified PET containing hydroxyl-terminated or carboxyl-terminated PET prepared in step (1) in a solvent to make a 20%~50% solution, and then add a 1:1 reaction amount of React the vinyl monomer with the terminal hydroxyl reactive group for 4 hours in an ice-water bath; or add a 1:1 reaction amount of the vinyl monomer containing the reactive group with the terminal carboxyl group according to the molar amount of the terminal carboxyl group, at 60~120°C Reaction 6 h;

(3) Wash and filter the macromonomer containing the modified PET chain segment obtained in step (2), put it in a vacuum drying oven for 24 hours, and then carry out a copolymerization reaction with the vinyl monomer in proportion; or mix the modified PET chain segment The macromonomer solution directly reacts with the vinyl monomer in proportion to the copolymerization reaction.

Wherein, the preparation method of the hydroxyl-terminated or carboxyl-terminated PET is as follows: under the protection of _N2 , terephthalic acid, ethylene glycol and functional monomers are reacted under vacuum at 200-280° C. for 2-6 hours. Functional monomers are oily functional monomers: adipic acid, phthalic anhydride, maleic anhydride, hexanediol, azelaic acid, sebacic anhydride, isophthalic acid, propylene glycol, butylene glycol, neopentyl glycol, hexanediol one or more of.

Further, the molar ratio of the total hydroxyl groups to the total carboxyl groups in the terephthalic acid, the ethylene glycol and the functional monomers is 1.2-1.8:1. Since ethylene glycol is volatile, in order to make the molar ratio of total hydroxyl groups and total carboxyl groups participating in the reaction to be 1:1, it is necessary to input excess hydroxyl raw materials. When the molar ratio of the total hydroxyl groups participating in the reaction to the total carboxyl groups is 1:1, it is beneficial to obtain a modified PET with one terminal hydroxyl group and the other terminal carboxyl group.

Further, the solvent in step (2) includes toluene, xylene, ethyl acetate, butyl acetate, butanone, methylene chloride, ethylene dichloride, dimethylformamide, dimethyl sulfoxide, water, ethanol , acetone, tetrahydrofuran in one or more.

The third object of the present invention is to provide an application of acrylate graft modified PET copolymer. The application of the above-mentioned acrylate graft-modified PET copolymer is as a water-based or oily PET bottom coating, a PET coating, and a printing ink.

Further, after diluting the acrylate graft-modified PET copolymer with a solvent to a solid content of 5% to 25%, it is used as a PET coating or printing ink. The acrylate graft-modified PET copolymer can provide the same functional side chain as the PET substrate, and the coating or ink has good adhesion to the PET substrate, and is suitable for use as a coating or ink on the PET surface. Dilute the acrylate graft-modified PET copolymer with the solvent to a solid content of 1% to 5%, which can be used alone as a primer for the PET substrate and directly coated on the surface of the PET substrate to Improve the adhesion between PET substrates, coatings and printing inks.

The fourth object of the present invention is to provide a coating comprising the above-mentioned acrylate graft-modified PET copolymer, including the acrylate graft-modified PET copolymer solution, leveling agent, defoamer, coating additive, Pigments or dyes.

The fifth object of the present invention is to provide a kind of ink comprising the above-mentioned acrylate graft modified PET copolymer, including the acrylate graft modified PET copolymer solution, leveling agent, defoamer, ink auxiliary agent, Pigments or dyes.

Due to the special design of the structure of the present invention, the acrylate graft-modified PET copolymer has hydrophilicity or lipophilicity, and the acrylate graft-modified PET copolymer can be used as a coating or printing ink for PET substrates. The PET substrate has good adhesion; at the same time, the obtained acrylate graft modified PET copolymer is dissolved in an organic solvent or water and used as a bottom coating of PET to improve the adhesion of coatings and printing inks to the PET substrate.

Compared with the prior art, the present invention modifies the acrylic polymer by adding macromolecular functional monomers, which can improve the adhesion of coatings and inks on the PET surface, and can be used as PET coatings and inks to make coatings and inks stick to PET surfaces. The surface adhesion is greatly improved, it is not easy to fall off, and the durability is good, which improves the surface printing and coating performance of PET substrates. Moreover, the process is simple, the cost is low, and PET does not need surface treatment; it has huge application prospects and market value.

Description of drawings

Fig. 1 is the structural representation of acrylate graft modified PET copolymer;

Fig. 2 is the infrared spectrogram of acrylate graft modified PET copolymer.

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings.

Example 1

In a dry 500mL four-neck flask, add 200g terephthalic acid, 10g adipic acid, 60g neopentyl glycol, and 150mL ethylene glycol in sequence, turn on the mechanical stirring and blow nitrogen for 10 minutes to remove oxygen. Add 0.413mL tetrabutyl titanate and mix well. Stir and heat up slowly, the temperature of the material is controlled at 220~240°C for 4 hours; the temperature is lowered to 220°C, stirred and reacted for 3 hours under high vacuum, and the material is discharged while it is hot to obtain a modified PET with a hydroxyl group at one end and a carboxyl group at the other end. The obtained modified PET polymer having one terminal hydroxyl group and the other terminal carboxyl group had a molecular weight of 1000 g/mol and a hydroxyl value of 57.3 mgKOH/g.

Dissolve 100 g of modified PET with a hydroxyl terminal at one end and a carboxyl terminal at the other end in 400 mL of N,N dimethylformamide, add acryloyl chloride in a 1:1 reaction amount according to the molar amount of the hydroxyl group, react in an ice-water bath for 4 hours, add Wash with saturated brine, the product is insoluble in water, filter it with suction, and put it in a vacuum oven for 24 hours. A macromonomer containing a modified PET chain segment is obtained.

The above-mentioned 25g macromer, 325g methyl methacrylate, 50g butyl methacrylate, and 100g ethyl acrylate were added to a 2000 mL four-necked flask, and 500 mL butyl acetate and 10 g benzoyl peroxide were added. At 80 °C for 6 h, a acrylate graft-modified PET copolymer solution with a solid content of 50% was obtained.

Use a mixed solvent of toluene, ethyl acetate, and butyl acetate to dilute the acrylate graft-modified PET copolymer with a solid content of 50% to a solid content of 25%, add 1g BYK-052 defoamer and 0.5g BYK- 300 leveling agent, coating additives and pigments; stir evenly and apply on the surface of PET board. The adhesion of the coating is measured by the cross-cut method of GB9286-98, and the adhesion of the paint on PET is good, reaching 0-1 grade.

Example 2

In a dry 1000mL four-neck flask, add 400g of terephthalic acid, 20g of adipic acid, 60g of neopentyl glycol, and 300mL of ethylene glycol in sequence, turn on mechanical stirring and blow nitrogen for 10 minutes to remove oxygen. Add 0.481mL tetrabutyl titanate and mix well. Stir and slowly heat up to 250°C for 3h. Cool down to 200°C, stir and react under high vacuum for 6h, and discharge while hot. The obtained modified PET polymer having a hydroxyl terminal at one end and a carboxyl terminal at the other end has a molecular weight of 2000 g/mol and a hydroxyl value of 28.2 mgKOH/g.

Dissolve 100 g of modified PET with a hydroxyl terminal at one end and a carboxyl terminal at the other end in 400 mL of N,N dimethylformamide, add 1:1 reaction amount of methacryloyl chloride according to the molar amount of the hydroxyl group, and react in an ice-water bath for 4 hours , adding saturated brine to wash, the product is insoluble in water, filtered with suction, and put into a vacuum drying oven for 24h. A macromonomer containing a modified PET chain segment is obtained.

The above-mentioned 50g macromer, 400g methyl methacrylate, and 50g butyl acrylate were added into a 2000 mL four-neck flask, and 500 mL butyl acetate and 9 g benzoyl peroxide were added. At 80°C for 8 h, a acrylate graft-modified PET copolymer solution with a solid content of 50% was prepared.

Use ethyl acetate, butyl acetate, toluene mixed solvent to dilute the acrylate graft modified PET copolymer with a solid content of 50% to a solid content of 5%, add 1g BYK-052 defoamer and 0.5g BYK- 300 Leveling agent, coating additives and dyes, stir evenly, and apply on the surface of PET board. The adhesion of the coating is measured by the cross-cut method of GB9286-98, and the adhesion of the paint on PET is good, reaching 0-1 grade.

Example 3

In a dry 1000mL four-neck flask, add 237g terephthalic acid, 76g adipic acid, 58g neopentyl glycol, and 259mL ethylene glycol in sequence, start mechanical stirring and blow nitrogen for 10 minutes to remove oxygen. Add 0.55mL tetrabutyl titanate and mix well. Stir and heat up slowly, and the material temperature is controlled at 220°C for 5 hours. Vacuumize, raise the temperature to 230°C for 4 hours, and cool down to prepare a modified PET polymer with terminal hydroxyl groups at one end and carboxyl terminal groups at the other end. The molecular weight of the obtained modified PET polymer containing terminal hydroxyl group and the other terminal carboxyl group was 10000 g/mol, and the hydroxyl value was 5.6 mgKOH/g.

Dissolve 100 g of modified PET with a terminal hydroxyl group at one end and a carboxyl terminal group at the other end in 400 mL of N,N dimethylformamide, add 1:1 reaction amount of p-chloromethyl styrene according to the molar weight of the hydroxyl group, and dissolve at 40 React at ℃ for 4 hours, add saturated brine to wash, the product is insoluble in water, filter it with suction, and put it in a vacuum oven for 24 hours. A macromonomer containing a modified PET chain segment is obtained.

Add the above 25g macromer, 380g methyl methacrylate, 25g ethyl acrylate, 20g butyl acrylate, and 50g styrene into a 2000 mL four-neck flask, add 500 mL N,N dimethylformamide and 5g dimethylacetate Azodiisobutyronitrile. At 70 °C for 4 h, a acrylate graft-modified PET copolymer solution with a solid content of 50% was prepared.

Dilute the acrylate graft-modified PET copolymer with a solid content of 50% to a solid content of 1% with a mixed solvent of ethyl acetate, butyl acetate, and toluene, and use it alone as a primer for PET substrates. The adhesion of the coating is measured by the cross-cut method of GB9286-98, and the adhesion of the paint on PET is good, reaching 0-1 grade.

Example 4

In a dry 1000mL four-neck flask, add 268g of terephthalic acid, 76g of adipic acid, 33g of propylene glycol, and 250mL of ethylene glycol in sequence, turn on the mechanical stirring and blow nitrogen for 10 minutes to remove oxygen. Add 0.688mL tetrabutyl titanate and mix well. Stir and heat up slowly, control the temperature of the material below 180°C, and react for 6 hours; add 0.25mL of triphenyl phosphite, slowly heat up to 255°C, vacuumize and stir for 4 hours, and discharge the material while it is hot. The prepared end contains a terminal hydroxyl group and the other end The molecular weight of the modified PET polymer containing terminal carboxyl groups is 6000 g/mol, and the acid value is 9.5 mgKOH/g.

Dissolve 100 g of modified PET with a hydroxyl terminal at one end and a carboxyl terminal at the other end in 400 mL of N,N dimethylformamide, add a 1:1 reaction amount of glycidyl methacrylate according to the molar weight of the carboxyl group, and dissolve at 60 It was reacted at ℃ for 6 hours, washed with saturated brine, filtered with suction, and put into a vacuum oven for 24 hours. A macromonomer containing a modified PET chain segment is obtained.

Add the above 75g macromer, 250g methyl methacrylate, 100g sodium vinyl sulfonate, 50 g butyl methacrylate, and 25 g hydroxyethyl acrylate into a 2000 mL four-necked flask, and add 500 mL N,N dimethyl Dimethyl formamide and 8g of azobisisobutyronitrile. At 70 °C for 8 h, a acrylate graft-modified PET copolymer solution with a solid content of 50% was prepared.

The acrylate graft-modified PET copolymer with a solid content of 50% is diluted to a solid content of 5% with a mixed solvent of water and ethanol, and is used alone as a primer for a PET substrate. The adhesion of the coating is measured by the cross-cut method of GB9286-98, and the adhesion of the paint on PET is good, reaching 0-1 grade.

Example 5

In a dry 1000 mL four-neck flask, sequentially add 235 g of terephthalic acid, 200 g of ethylene glycol, 48 g of adipic acid, and 63 g of neopentyl glycol, and mix and stir for 15 min to remove oxygen under the protection of _N2 ; then add tin oxide 3g, mixed evenly, heated to 240°C, stirred and reacted for 2h; vacuumed and stirred for 4h, discharged while hot. The obtained modified PET polymer having a terminal hydroxyl group at one end and a carboxyl terminal at the other end has a molecular weight of 800 g/mol and an acid value of 70 mgKOH/g.

Dissolve 100 g of modified PET with a hydroxyl terminal at one end and a carboxyl terminal at the other end in 400 mL of N,N dimethylformamide, add glycidyl acrylate in a reaction amount of 1:1 according to the molar amount of carboxyl groups, and react at 120°C 6h, wash and filter. A macromonomer containing a modified PET chain segment is obtained.

Add the above 200g macromer solution, 315g methyl methacrylate, 50g butyl acrylate, 15g ethyl methacrylate, and 80g styrene into a 2000 mL four-necked flask, add 340 mL butyl acetate and 5g benzene peroxide formyl. At 80°C for 8 h, a acrylate graft-modified PET copolymer solution with a solid content of 50% was prepared.

Use solvent ethyl acetate, butyl acetate, dimethylformamide mixed solvent to dilute the acrylic acid ester graft-modified PET copolymer that solid content is 50% to solid content and be 15%, add the oily color paste that grinds, disinfectant Foaming agent, leveling agent, 1g BYK-3520 multifunctional additive, stir well. Print on the surface of PET board, measure the adhesion with GB9286-98 cross-cut method, the adhesion of the ink on PET is good, reaching 0-1 level.

Example 6

In a dry 500mL four-neck flask, sequentially add 150g of terephthalic acid, 100g of ethylene glycol, 15g of diethylene glycol, and 25g of dipropylene glycol, and mix and stir for 15 minutes to remove oxygen under the protection of _N2 ; then add 6g of antimony trioxide, mixed evenly, heated to reflux at 250°C, stirred and reacted for 3h; cooled to below 230°C, vacuumed and reacted for 4h. The molecular weight of the prepared modified PET containing terminal hydroxyl group and the other terminal carboxyl group was 15000 g/mol, and the hydroxyl value was 4 mgKOH/g.

Dissolve 100 g of modified PET with a hydroxyl terminal at one end and a carboxyl terminal at the other end in 400 mL of N,N dimethylformamide, add 1:1 reaction amount of methacrylic acid chloride according to the molar amount of the hydroxyl group, and react at 0°C After 4 hours, add saturated brine to wash, filter with suction, and put into a vacuum drying oven for 24 hours. A macromonomer containing a modified PET chain segment is obtained.

Put the above 100g macromer, 250g methyl methacrylate, 50g butyl methacrylate, 20g acrylic acid, 55g sodium vinyl sulfonate, 25g vinyl acetate into a 2000 mL four-necked flask, add 500 mL N, N two Methylformamide and 10g benzoyl peroxide. At 80 °C for 6 h, a acrylate graft-modified PET copolymer solution with a solid content of 50% was prepared.

Use the solvent acetone and dimethylformamide to dilute the acrylate graft-modified PET copolymer with a solid content of 50% to a solid content of 20%, and add the ground water-based color paste and additives. Printed on the surface of the PET board, the adhesion is measured by the GB9286-98 cross-cut method, the adhesion of the ink coating on the PET is good, reaching 0-1 grade.

Example 7

In a dry 500mL four-necked flask, add terephthalic acid and ethylene glycol at a molar ratio of 1:1, then add diethylene glycol and dipropylene glycol, and mix and stir for 15 minutes to remove oxygen under the protection of _N2 ; Then add 6g of antimony trioxide, mix well, heat to 250°C to reflux, stir for 3h; cool down to below 230°C, and vacuum for 4h. The molecular weight of the prepared modified PET polymer with a hydroxyl-terminated end and a carboxyl-terminated end is 15000 g/mol.

Dissolve 100 g of modified PET with a hydroxyl-terminated end and a carboxyl-terminated PET in 400 mL of N,N dimethylformamide, add 1:1 reaction amount of methacrylic acid chloride according to the molar amount of the hydroxyl group, and react at 0°C for 4 hours , washed with saturated brine, filtered with suction, and placed in a vacuum oven for 24 hours. A macromonomer containing a modified PET chain segment is obtained.

Add the above 4g macromer, 250g methyl methacrylate, 50g butyl methacrylate, 20g acrylic acid, 51g sodium vinyl sulfonate, 25g vinyl acetate into a 2000 mL four-neck flask, add 500 mL N,N Dimethylformamide and 10g benzoyl peroxide. At 80 °C for 6 h, a acrylate graft-modified PET copolymer solution with a solid content of 50% was obtained.

Use the solvent acetone and dimethylformamide to dilute the acrylate graft-modified PET copolymer with a solid content of 50% to a solid content of 20%, and add the ground water-based color paste and additives. Printed on the surface of the PET board, the adhesion is measured by the GB9286-98 cross-cut method, the adhesion of the ink coating on the PET is good, reaching 0-1 grade.

The acrylate graft-modified PET copolymer prepared according to the method described in Examples 1-7 carried out infrared characterization, as shown in Figure 2, the acrylate graft-modified PET copolymer was obtained, and the obtained acrylate graft-modified The schematic diagram of the structure of PET copolymer is shown in Figure 1, and the molecular weight is 8000~80000.

The above disclosures are only preferred embodiments of the present invention, and certainly cannot limit the scope of rights of the present invention. Therefore, equivalent changes made according to the claims of the present invention still fall within the scope of the present invention.

Claims (14)

1. a kind of acrylic ester grafted modified PET copolymer, which is characterized in that by the modified PET containing terminal hydroxy group or end carboxyl It prepares and contains with the vinyl monomer reaction containing the group that can be reacted with terminal hydroxy group or containing the group that can be reacted with end carboxyl After the macromonomer of modified PET segment, then with vinyl monomer copolymerization；The acrylic ester grafted modified PET copolymerization Object molecular weight is 8000 ~ 80000 g/mol；Macromonomer weight percentage composition described in copolyreaction is 1 ~ 20%；

The vinyl monomer is methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate, methyl methacrylate Ester, ethyl methacrylate, butyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, acrylic acid, glycidyl acrylate, propylene A variety of in sour hydroxyl ethyl ester, methacrylic acid, glycidyl methacrylate, hydroxyethyl methacrylate or its further With the mixing of styrene or/and vinylacetate or/and sodium styrene sulfonate.

2. acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that the segment containing modified PET Macromonomer be the segment containing modified PET acrylic ester type macromonomer, the methacrylate of the segment containing modified PET One or more in type macromonomer or it is further mixed with the styrene type macromonomer of the segment containing modified PET It closes.

3. acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that it is described containing can with hold hydroxyl Base reaction group vinyl monomer for acrylic acid, acryloyl chloride, methacrylic acid, one kind in methacrylic chloride or A variety of or its further mixing with p-chloromethyl styrene or/and to bromometllylstyrene；It is described to contain energy and end carboxyl The vinyl monomer of the group of reaction is glycidyl acrylate, glycidyl methacrylate, hydroxy-ethyl acrylate, third One or more in olefin(e) acid hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate.

4. acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that described acrylic ester grafted Modified PET copolymer is oil-soluble, the oil containing 0%-5% water-soluble vinyl monomers and 95%-100% in the vinyl monomer Dissolubility vinyl monomer.

5. acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that described acrylic ester grafted Modified PET copolymer is water solubility, containing 60%-90% oil-soluble ethylene base monomers and 10%-40% in the vinyl monomer Water-soluble vinyl monomer.

6. acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that it is described containing terminal hydroxy group or The modified PET of end carboxyl contains the modified PET that the terminal hydroxy group other end contains end carboxyl for one end.

7. according to the preparation method of any one of the claim 1-6 acrylic ester grafted modified PET copolymers, feature exists In mainly including the following steps that：

（1）Prepare the modified PET containing terminal hydroxy group or end carboxyl；

（2）By step（1）The modified PET containing terminal hydroxy group or end carboxyl prepared is dissolved in solvent, is made into 20% ~ 50% solution, 1 is added in according still further to the mole of terminal hydroxy group:Containing for 1 reacting dose can be with the vinyl monomer of terminal hydroxy group reactive group, ice-water bath React 4h；Or add in 1 according to the mole of end carboxyl:1 reacting dose containing can with the vinyl monomer of end carboxyl reactive group, 6 h are reacted in 60 ~ 120 DEG C；

（3）By step（2）Gained segment containing modified PET macromonomer washing, filtering after be put into vacuum drying chamber for 24 hours after with Vinyl monomer proportionally carries out copolyreaction；Or by the macromonomer solution of the segment containing modified PET directly and vinyl Monomer proportionally carries out copolyreaction.

8. preparation method according to claim 7, which is characterized in that the preparation side of the terminal hydroxy group or end carboxyl modified PET Method is：By terephthalic acid (TPA), ethylene glycol and function monomer in N₂Protection under vacuumized in 200-280 DEG C and be stirred to react 2-6h.

9. preparation method according to claim 8, which is characterized in that the terephthalic acid (TPA), the ethylene glycol and the work( The molar ratio of total hydroxyl and total carboxyl is 1.2-1.8 in energy monomer：1.

10. preparation method according to claim 7, which is characterized in that step（2）The solvent includes toluene, dimethylbenzene, second Acetoacetic ester, butyl acetate, butanone, dichloromethane, dichloroethanes, dimethylformamide, dimethyl sulfoxide, water, ethyl alcohol, acetone, four One or more in hydrogen furans.

11. the application of acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that as aqueous or PET bottom coverings, PET coating, the printing ink of person's oiliness.

12. the application of acrylic ester grafted modified PET copolymer according to claim 11, which is characterized in that with described molten The acrylic ester grafted modified PET copolymer is diluted to amount of solid content as after 5% ~ 25% by agent, as PET coating or print Brush ink；It is 1% ~ 5% that the acrylic ester grafted modified PET copolymer is diluted to amount of solid content with the solvent, individually Subbing as PET base material uses.

A kind of 13. coating for including acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that bag Include the acrylic ester grafted modified PET copolymer solution, levelling agent, antifoaming agent, coating additive, pigment or dyestuff.

A kind of 14. ink for including acrylic ester grafted modified PET copolymer according to claim 1, which is characterized in that bag Include the acrylic ester grafted modified PET copolymer solution, levelling agent, antifoaming agent, ink addition agent, pigment or dyestuff.