Acrylate modified polyester resin as well as preparation method and application thereof

Abstract

The invention relates to acrylate modified polyester resin as well as a preparation method and application thereof. The method comprises the following steps: (1) performing esterification reaction on anhydride with polyfunctional groups and long-chain unsaturated monofunctional alcohol to obtain an unsaturated intermediate; (2) carrying out esterification reaction on the unsaturated intermediate obtained in the step (1), dibasic acid and dihydric alcohol, and then carrying out polycondensation reaction to obtain a polyester resin intermediate containing unsaturated double bonds; and (3) carrying out free radical polymerization reaction on the polyester resin intermediate containing the unsaturated double bond obtained in the step (2) and an acrylate monomer to obtain the acrylate modified polyester resin. The acrylate modified polyester resin obtained by the method provided by the invention has excellent non-polar base material bonding performance.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and in particular to an acrylate modified polyester resin and a preparation method and application thereof. Background Art

[0002] PP (polypropylene) and PE (polyethylene), as non-polar polymer materials, are widely used in construction, automotive, electronics, packaging, medical and other fields due to their excellent chemical stability, corrosion resistance, light weight and low cost. However, their non-polar molecular structure leads to extremely poor bonding performance, which has become a long-standing technical bottleneck in industrial applications. PP / PE is composed only of carbon and hydrogen atoms and lacks polar groups (such as hydroxyl and carboxyl groups). It cannot form chemical bonds or hydrogen bonds with conventional adhesives, resulting in insufficient interfacial bonding strength. In addition, its surface energy is only 30-34mN / m, making it difficult for glue to wet and spread. Contact angle tests show that the liquid easily shrinks into a spherical shape.

[0003] CN104893648B discloses a polyamide hot melt adhesive with strong adhesion to non-polar materials. The adhesive is prepared using aliphatic diamines, alicyclic diamines, polyamides, dimer acids, and silane coupling agents. This patent significantly improves the bonding efficiency to non-polar materials and shortens the open time by controlling the dimer acid-based polyamide formula of each component and a precise polycondensation process. However, the formula uses a variety of special monomers, which undoubtedly increases the raw material cost. It also has disadvantages such as a complex preparation process. CN 119505739A utilizes a large amount of {C2H4} n The chain segments achieve good wetting and adhesion to low-polarity substrates, solving the problem of difficult adhesion of low-surface-energy materials. However, it uses pure acrylic acid monomers as raw materials and undergoes free radical polymerization. Its molecular weight is difficult to control and tends to be too large, which has a certain impact on subsequent applications.

[0004] Therefore, there is an urgent need to develop a structural polyester with simple and controllable process, which can be used as the main body to synthesize non-polar substrate adhesive to solve the problem of low adhesion to non-polar substrate PP / PE. Summary of the Invention

[0005] In order to overcome the above-mentioned defects of the prior art, the present invention aims to provide an acrylate-modified polyester resin having excellent bonding properties to low surface energy materials and a preparation method thereof.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A first object of the present invention is to provide a method for preparing an acrylate-modified polyester resin, the method comprising the following steps:

[0008] (1) An acid anhydride with multiple functional groups reacts with a long-chain unsaturated monofunctional alcohol to produce an unsaturated intermediate;

[0009] (2) subjecting the unsaturated intermediate obtained in step (1) to an esterification reaction with a dibasic acid and a diol, and then subjecting the resultant to a polycondensation reaction to obtain a polyester resin intermediate containing an unsaturated double bond;

[0010] (3) subjecting the polyester resin intermediate containing unsaturated double bonds obtained in step (2) to a free radical polymerization reaction with an acrylate monomer to obtain the acrylate-modified polyester resin;

[0011] Wherein, the acid anhydride having multiple functional groups is selected from trimellitic anhydride and / or pyromellitic dianhydride;

[0012] The long-chain unsaturated monofunctional alcohol is selected from the compound represented by formula (I):

[0013]

[0014] Wherein, R1 is an alkane chain segment having more than 6 carbon atoms.

[0015] Preferably, R1 is an alkane segment having 6 to 22 carbon atoms, preferably an alkane segment having 6 to 12 carbon atoms;

[0016] Preferably, the long-chain unsaturated monofunctional alcohol is selected from one or more of 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol and 11-dodecen-1-ol.

[0017] Preferably, in step (1), the molar ratio of the anhydride groups in the acid anhydride having multiple functional groups to the hydroxyl groups in the long-chain unsaturated monofunctional alcohol is 1 to 1.1:1.

[0018] Preferably, in step (3), the acrylate monomer is selected from the compound represented by formula (II):

[0019]

[0020] wherein R2 is selected from hydrogen and C 1～6 Alkyl;

[0021] R3 is a straight or branched alkane chain segment having more than 10 carbon atoms.

[0022] Preferably, R2 is selected from hydrogen and C 1～3 The alkyl group is preferably hydrogen or methyl;

[0023] The R3 is a straight chain or branched alkane segment having 10 to 30 carbon atoms, preferably a straight chain or branched alkane segment having 10 to 22 carbon atoms;

[0024] Preferably, the acrylate monomer is selected from one or more of isodecyl acrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate and behenyl acrylate.

[0025] Preferably, the molar ratio of the acrylic acid ester monomer to the long-chain unsaturated monofunctional alcohol is 0.6-0.8:1.

[0026] Preferably, in step (2), the molar ratio of the long-chain unsaturated monofunctional alcohol to the dibasic acid is 0.5 to 0.8:1;

[0027] Preferably, the molar ratio of the diol: the dibasic acid and the acid anhydride having multiple functional groups is 1.3 to 2.0:1.

[0028] Preferably, the dibasic acid is selected from one or more of terephthalic acid, isophthalic acid, adipic acid, sebacic acid and dimer acid;

[0029] Preferably, the diol is selected from one or more of ethylene glycol, butanediol, 2-methyl-1,3-propanediol and hexanediol.

[0030] The second object of the present invention is to provide an acrylate-modified polyester resin obtained according to any one of the preparation methods described above.

[0031] The third object of the present invention is to provide an acrylate-modified polyester resin obtained according to any one of the preparation methods described above, or use of the acrylate-modified polyester resin described above in a non-polar substrate.

[0032] Effects of the Invention

[0033] The present invention uses an acid anhydride with multiple functional groups and a long carbon chain unsaturated monofunctional alcohol as raw materials to synthesize an unsaturated intermediate monomer, and then further esterifies and polycondenses the intermediate monomer with a conventional dibasic acid and a diol to obtain a polyester resin intermediate containing an unsaturated double bond. Subsequently, an acrylate monomer is grafted into the resin intermediate system to obtain a modified resin with strong bonding properties to non-polar substrates (such as PP or PE materials).

[0034] The preparation process provided by the present invention is stable and controllable, with advantages such as controllable molecular weight, solubility in a mixed solution of toluene and butanone, a transparent and uniform solution state, and storage stability. Furthermore, the polyester resin obtained by the present invention can be blended with conventional polyesters (or) and isocyanates to produce an adhesive with excellent adhesion to low-surface-energy substrates, a uniform and transparent appearance, and good chemical resistance. DETAILED DESCRIPTION

[0035] In order to make the technical solutions and beneficial effects of the present invention more obvious and easy to understand, the following is a detailed description by listing specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Any product that is identical or similar to the present invention and is obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts falls within the scope of protection of the present invention. Unless otherwise defined, the technical and scientific terms used herein have the same meaning as those in the technical field to which this application belongs.

[0036] If no specific techniques or conditions are specified in the following examples, the experiments were generally carried out in accordance with conventional techniques or conditions described in the literature in the art, or in accordance with the product instructions and the conditions recommended by the manufacturer.

[0037] Unless otherwise indicated, various starting materials, materials and reagents were either commercially available or synthesized according to known methods.

[0038] A first object of the present invention is to provide a method for preparing an acrylate-modified polyester resin, the method comprising the following steps:

[0039] (1) An acid anhydride with multiple functional groups reacts with a long-chain unsaturated monofunctional alcohol to produce an unsaturated intermediate;

[0040] (2) subjecting the unsaturated intermediate obtained in step (1) to an esterification reaction with a dibasic acid and a diol, and then subjecting the resultant to a polycondensation reaction to obtain a polyester resin intermediate containing an unsaturated double bond;

[0041] (3) subjecting the polyester resin intermediate containing unsaturated double bonds obtained in step (2) to a free radical polymerization reaction with an acrylate monomer to obtain the acrylate-modified polyester resin;

[0042] Wherein, the acid anhydride having multiple functional groups is selected from trimellitic anhydride and / or pyromellitic dianhydride;

[0043] The long-chain unsaturated monofunctional alcohol is selected from the compound represented by formula (I):

[0044]

[0045] Wherein, R1 is an alkane chain segment having a carbon number greater than 6. In the present invention, the long-chain unsaturated monofunctional alcohol has a carbon number greater than 6 and a carbon chain that is too short and has a low boiling point, and cannot participate in the system reaction.

[0046] In one embodiment, R1 is an alkane segment having 6 to 22 carbon atoms, such as 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

[0047] In one embodiment, R1 is an alkane segment having 6 to 12 carbon atoms.

[0048] In one embodiment, the long-chain unsaturated monofunctional alcohol is selected from one or more of 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol and 11-dodecen-1-ol.

[0049] In one embodiment, in step (1), the molar ratio of the anhydride groups in the acid anhydride having a multifunctional group to the hydroxyl groups in the long-chain unsaturated monofunctional alcohol is 1 to 1.1:1, for example, 1:1, 1.01:1, 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, and 1.1:1.

[0050] In one embodiment, in step (1), the molar ratio of the anhydride groups in the acid anhydride having multiple functional groups to the hydroxyl groups in the long-chain unsaturated monofunctional alcohol is 1.01 to 1.08:1.

[0051] In the present invention, the esterification reaction can be carried out in the presence of a catalyst well known to those skilled in the art. In the present invention, the type of catalyst is not limited, as long as it can smoothly carry out and complete the above reaction. In the present invention, examples of suitable catalysts include, but are not limited to, those based on titanium, tin, gallium, zinc, antimony, cobalt, manganese, germanium, alkali metals (particularly lithium and sodium), alkaline earth metal compounds, aluminum compounds, combinations of aluminum compounds with lithium hydroxide or sodium hydroxide, and mixtures thereof. In a certain embodiment, the catalyst is based on titanium or tin.

[0052] Examples of suitable titanium compounds include tetraisopropyl titanate, bis(acetylacetonato)diisopropyl titanate, and tetrabutyl titanate.Examples of suitable tin compounds include butyltin tri-2-ethylhexanoate, butylstannoic acid, stannous oxalate, dibutyltin oxide.

[0053] In one embodiment, in step (2), the molar ratio of the long-chain unsaturated monofunctional alcohol to the dibasic acid is 0.5 to 0.8:1, for example, 0.55:1, 0.60:1, 0.65:1, 0.70:1, 0.75:1, or 0.80:1.

[0054] In one embodiment, the molar ratio of the diol: the dibasic acid and the acid anhydride having multiple functional groups is 1.3 to 2.0:1, for example, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2:1.

[0055] In one embodiment, the molar ratio of the diol to the dibasic acid is 1.5 to 3.5:1, for example, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, and 3.5:1.

[0056] In one embodiment, the dibasic acid is selected from one or more of terephthalic acid, isophthalic acid, adipic acid, sebacic acid and dimer acid.

[0057] In one embodiment, the diol is selected from one or more of ethylene glycol, butanediol, 2-methyl-1,3-propanediol and hexanediol.

[0058] In the present invention, the polycondensation reaction in step (2) can be carried out in the presence of a stabilizer well known to those skilled in the art. In the present invention, the type of stabilizer is not limited, as long as it can allow the above reaction to proceed smoothly. In the present invention, a suitable stabilizer is a phosphorus-based stabilizer. Examples of suitable phosphorus-based stabilizers include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and triethyl phosphonoacetate. Step (2) obtains an unsaturated polyester matrix resin with a long side chain, and the double bond position is located at the end of the side chain, which has high reactivity.

[0059] In one embodiment, in step (3), the acrylate monomer is selected from the compound represented by formula (II):

[0060]

[0061] wherein R2 is selected from hydrogen and C 1～6 Alkyl;

[0062] R3 is a straight or branched alkane chain segment having more than 10 carbon atoms.

[0063] In one embodiment, R2 is selected from hydrogen and C 1～3 of alkyl.

[0064] In one embodiment, R2 is hydrogen or methyl;

[0065] In one embodiment, R3 is a straight or branched alkane segment having 10 to 30 carbon atoms. The present invention further reduces the polarity of the overall polyester by controlling the number of C atoms of the long carbon chain acrylate to be greater than or equal to 10, thereby further improving the adhesion performance of the polyester resin to substrates with low surface energy.

[0066] In one embodiment, the R3 is a straight or branched alkane chain segment having 10 to 22 carbon atoms.

[0067] In one embodiment, the acrylate monomer is selected from one or more of isodecyl acrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, and behenyl acrylate.

[0068] In one embodiment, the molar ratio of the acrylate monomer to the long-chain unsaturated monofunctional alcohol is 0.6 to 0.8:1, for example, 0.61, 0.62, 0.63, 0.64, 0.65, 0.67, 0.68, 0.69, 0.7, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.80, etc.

[0069] In the present invention, the grafting reaction of the acrylate monomer can be carried out in the presence of a solvent and an initiator well known to those skilled in the art. The type of initiator is not limited in the present invention, as long as it allows the above reaction to proceed smoothly. In the present invention, suitable initiators are azo compounds or peroxides.

[0070] Examples of suitable azo compounds include azobisisobutyronitrile (AIBN), azobiscyanovaleric acid (ACVA), 1,1′-azobis(cyclohexanecarbonitrile) (ACHN), α-phenylazotriphenylmethane.

[0071] Examples of suitable peroxides include dibenzoyl peroxide, dicumyl peroxide, diacetyl peroxide, dilauryl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoic acid.

[0072] In the present invention, the suitable solvent is selected from one or more of a ketone solvent, an aromatic hydrocarbon solvent, and an ester solvent. Examples of suitable aromatic hydrocarbon solvents include toluene. Examples of suitable ester solvents include ethyl acetate and butyl acetate. Examples of suitable ketone solvents include butanone.

[0073] There are no particular restrictions on the operating temperature and time in the above steps (1) to (3), as long as the reaction can be smoothly carried out and completed. For example, in step (1), the esterification reaction to form the unsaturated intermediate can be carried out at about 130-200°C, preferably at 155-180°C; after the reaction is completed, the temperature is lowered to 90-110°C, preferably at 95-105°C; in step (2), the dibasic acid and diol are added to the system and the esterification reaction is carried out at 200-280°C, preferably at 230-245°C; then the polycondensation reaction is carried out at 180-260°C, preferably at 200-240°C; in step (3), the grafting reaction can be carried out at 60-100°C, preferably at 60-80°C.

[0074] The present invention adopts a step-by-step feeding method. Under nitrogen protection, a polyfunctional acid anhydride, a long carbon chain unsaturated monofunctional alcohol and a catalyst are first added in proportion into a stainless steel reactor. The reaction pressure is set to 0.1 MPa, the stirring rate is 60-100 r / min, and the temperature is increased at a rate of 1-2°C / min for esterification. When the maximum temperature reaches 155-180°C and the hydroxyl value of the sample is less than 5 mg KOH / g, a second feeding is performed, and the remaining diol and dibasic acid are added to the reactor. The temperature is continued to be raised to 230-245°C. When the temperature at the top of the reactor is lower than 90°C, a sample is taken for acid value testing. When the acid value is less than 10 mg KOH / g, the esterification is terminated.

[0075] Adding an auxiliary agent to the esterification product, maintaining the polycondensation temperature at 200-240°C, the stirring rate at 40-100 r / min, the vacuum degree less than 100 Pa, and polycondensing to the corresponding current power to obtain a polyester resin intermediate.

[0076] The polyester resin intermediate is dissolved in a mixed solvent of toluene and butanone to form a solution with a solid content of 50% to 60%. An initiator and a long-chain acrylic acid are added dropwise at a temperature of 60 to 100° C. to carry out a grafting reaction, thereby obtaining the acrylate-modified polyester resin of the present application.

[0077] The second object of the present invention is to provide an acrylate-modified polyester resin obtained according to any one of the preparation methods described above.

[0078] The third object of the present invention is to provide an acrylate-modified polyester resin obtained according to any one of the preparation methods described above, or use of the acrylate-modified polyester resin described above in a non-polar substrate.

[0079] The present invention is further illustrated below with reference to specific examples and comparative examples. Unless otherwise specified, the following examples generally follow conventional techniques or conditions described in literature in the art, or in accordance with product specifications and manufacturer recommendations. Unless otherwise indicated, all starting materials, materials, and reagents were commercially available or synthesized according to known methods.

[0080] Example 1

[0081] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 152.25g of trimellitic anhydride, 111.13g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.99g of terephthalic acid, 138.96g of adipic acid, 59.02g of ethylene glycol, and 28.56g of 2-Methyl-1,3-propanediol and 231.08 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0082] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0083] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 180.02g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated after maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent of toluene and butanone with a volume ratio of 1:1 was added to finally prepare a sample with a solid content of 40% for testing.

[0084] Example 2

[0085] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 116.55g of pyromellitic anhydride, 154.48g of 9-decen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1°C / min for esterification. The maximum temperature reached 170°C. When the hydroxyl value of the sample was less than 5mgKOH / g, a secondary feeding was performed. The temperature was lowered to 100°C. 53.26g of terephthalic acid, 35.51g of isophthalic acid, 78.09g of adipic acid, 108.07g of sebacic acid, 59.7g of ethylene glycol, and 38.52g of 2-Methyl-1,3-propanediol and 155.82 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0086] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 60r / min, and maintain vacuum degree less than 100Pa. Polycondensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0087] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 264.41g of docosyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated after maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) of toluene and butanone was added to finally prepare a sample with a solid content of 40% for testing.

[0088] Example 3

[0089] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 150.07g of trimellitic anhydride, 109.55g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 77.86g of terephthalic acid, 148.4g of adipic acid, 58.18g of ethylene glycol, and 28.16g of 2-Methyl-1,3-propanediol and 227.79 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0090] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0091] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 131.43g of lauryl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The mixtures were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining the mixture for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to prepare a sample with a final solid content of 40% for testing.

[0092] Example 4

[0093] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 169.34g of trimellitic anhydride, 123.61g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 58.57g of terephthalic acid, 115.92g of adipic acid, 43.77g of ethylene glycol, and 31.77g of 2-Methyl-1,3-propanediol and 257.02 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0094] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0095] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 200.23g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining the mixture for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0096] Example 5

[0097] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 152.25g of trimellitic anhydride, 111.13g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.99g of terephthalic acid, 138.96g of adipic acid, 59.02g of ethylene glycol, and 28.56g of 2-Methyl-1,3-propanediol and 231.08 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0098] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0099] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 154.3g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The mixtures were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) of toluene and butanone was added to finally prepare a sample with a solid content of 40% for testing.

[0100] Example 6

[0101] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 152.25g of trimellitic anhydride, 111.13g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.99g of terephthalic acid, 138.96g of adipic acid, 59.02g of ethylene glycol, and 28.56g of 2-Methyl-1,3-propanediol and 231.08 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0102] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0103] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 198.02g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0104] Example 7

[0105] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 150.19g of trimellitic anhydride, 120.45g of 9-decen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 77.92g of terephthalic acid, 137.09g of adipic acid, 58.22g of ethylene glycol, and 28.18g of 2-Methyl-1,3-propanediol and 227.96 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0106] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0107] The above-mentioned base resin was dissolved using a mixed solvent of toluene and butanone (volume ratio of 1:1) as the solvent to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 208.29g of docosyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated after maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0108] Example 8

[0109] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 152.25g of trimellitic anhydride, 111.13g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.99g of terephthalic acid, 138.96g of adipic acid, 59.02g of ethylene glycol, and 28.56g of 2-Methyl-1,3-propanediol and 231.08 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0110] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0111] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 133.34g of lauryl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The mixtures were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining the mixture for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0112] Comparative Example 1

[0113] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 151.73g of trimellitic anhydride, 113.46g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.72g of terephthalic acid, 138.5g of adipic acid, 58.82g of ethylene glycol, and 28.47g of 2-Methyl-1,3-propanediol and 230.3 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0114] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0115] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 179.41g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining the mixture for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0116] Comparative Example 2

[0117] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 158.77g of trimellitic anhydride, 105.79g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 82.37g of terephthalic acid, 120.76g of adipic acid, 61.55g of ethylene glycol, 29.79g of 2-Methyl-1,3-propanediol and 240.98 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0118] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain a vacuum of less than 100Pa. Polycondensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin. The sample reaction is prone to cross-linking, and multiple experiments are required to obtain the target sample.

[0119] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 187.73g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining the mixture for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0120] Comparative Example 3

[0121] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 144.82g of trimellitic anhydride, 105.72g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 75.14g of terephthalic acid, 158.63g of adipic acid, 56.14g of ethylene glycol, and 27.17g of 2-Methyl-1,3-propanediol and 232.38 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0122] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0123] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 171.24g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0124] Comparative Example 4

[0125] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 184.17g of trimellitic anhydride, 134.44g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 63.7g of terephthalic acid, 112.07g of adipic acid, 71.4g of ethylene glycol, 34.55g of 2-Methyl-1,3-propanediol and 199.67 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0126] Add 0.1g of trimethyl phosphate to the esterified product, maintain polycondensation at 220°C, stir at 80r / min, and maintain a vacuum of less than 100Pa. Polycondensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin. The existence of steric hindrance makes it difficult for the sample's Mn to increase, prolongs the polycondensation time, and increases side reactions.

[0127] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 217.77g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0128] Comparative Example 5

[0129] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 152.25g of trimellitic anhydride, 111.13g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.99g of terephthalic acid, 138.96g of adipic acid, 59.02g of ethylene glycol, and 28.56g of 2-Methyl-1,3-propanediol and 231.08 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0130] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0131] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 149.16g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated after maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0132] Comparative Example 6

[0133] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 152.25g of trimellitic anhydride, 111.13g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.99g of terephthalic acid, 138.96g of adipic acid, 59.02g of ethylene glycol, and 28.56g of 2-Methyl-1,3-propanediol and 231.08 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0134] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0135] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 210.88g of octadecyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The two solvents were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) was added to finally prepare a sample with a solid content of 40% for testing.

[0136] Comparative Example 7

[0137] In a 2L reactor, under nitrogen protection, a step-by-step feeding method was adopted. First, 152.25g of trimellitic anhydride, 111.13g of 8-nonen-1-ol and 0.1g of tetrabutyl titanate were added to the reactor. The reaction pressure was set to 0.1Mpa and the stirring rate was 100r / min. The temperature was raised at a rate of 1℃ / min for esterification. The maximum temperature reached 170℃. When the hydroxyl value of the sample was less than 5mgKOH / g, a second feeding was performed. The temperature was lowered to 100℃. 78.99g of terephthalic acid, 138.96g of adipic acid, 59.02g of ethylene glycol, and 28.56g of 2-Methyl-1,3-propanediol and 231.08 g of neopentyl glycol were added to the reactor with a stirring rate of 100 r / min. The temperature was raised at a rate of 1°C / min for esterification. The temperature was continued to rise to 235°C. When the temperature at the top of the reactor was lower than 90°C, samples were taken for acid value testing. Esterification was terminated when the acid value was less than 10 mg KOH / g.

[0138] Add 0.1g of trimethyl phosphate to the esterified product, maintain condensation at 220℃, stir at 80r / min, and maintain vacuum degree less than 100Pa. Condensation is performed until the hydroxyl value of the sample reaches 25-35mg KOH / g to obtain the matrix resin.

[0139] The above-mentioned base resin was dissolved in a mixed solvent of toluene and butanone (volume ratio of 1:1) to form a solution with a solid content of 60%. At 70°C, 10g of initiator AIBN was dissolved in 25g of a mixed solvent (toluene and butanone with a volume ratio of 1:1), and 102.22g of octyl acrylate was dissolved in 50g of a mixed solvent (toluene and butanone with a volume ratio of 1:1). The mixtures were added dropwise to carry out a grafting reaction. After the addition was completed, the reaction was terminated by maintaining the mixture for 2 hours. The solid content of the sample was tested, and a mixed solvent (toluene and butanone with a volume ratio of 1:1) of toluene and butanone was added to prepare a sample with a solid content of 40% for testing.

[0140] Test Case

[0141] The properties of the acrylate-modified polyester resins prepared in Examples 1 to 8 and Comparative Examples 1 to 7 were evaluated:

[0142] (1) The molecular weight, acid value, hydroxyl value, etc. of the acrylate-modified polyester resins prepared in Examples 1 to 8 and Comparative Examples 1 to 7 were tested. The testing method is as follows:

[0143] The molecular weight Mn was determined by gel chromatography using a Waters e2695, a 2414RI Detector, a Styragel HR3 5 μm 7.8*300 mm (THF) column, and chloroform as the mobile phase.

[0144] Acid value: GB / T 12008.5-2010 Plastics polyether polyols Part 5_Determination of acid value.

[0145] Hydroxyl value: GB / T 12008.3-2009 Plastics polyether polyols Part 3 - Determination of hydroxyl value.

[0146] (2) The adhesive properties of the acrylate-modified polyester resins prepared in Examples 1 to 8 and Comparative Examples 1 to 7 to non-polar substrates were tested:

[0147] The graft-modified solutions prepared in Examples 1 to 8 and Comparative Examples 1 to 7 are used to prepare an adhesive, and a certain proportion of high Tg polyester and curing agent are added. The high Tg polyester is selected from Hanhai New Materials AH640, AH651, CH449, etc., and the curing agent is selected from HDI such as Bayer N3300, N3390, Asahi Kasei TPA-100, TMA-100, etc. The specific adhesive preparation method is as follows:

[0148] The high Tg polyester is dissolved in a mixed solvent of toluene and butanone (volume ratio is 1:1) to form a solution with a solid content of 40%. The high Tg polyester used in the present invention is AH640;

[0149] 80 parts of the grafted modified solution prepared in Examples 1 to 8 and Comparative Examples 1 to 7 were selected.

[0150] 15 parts of AH640 solution

[0151] N3300 5 copies

[0152] Stir evenly at room temperature and set aside.

[0153] Each adhesive was used to bond non-polar substrate PP / PE, with a substrate thickness of 40 μm and a glue amount of 10 g / m 2 , dried at 120℃ for 20s, composited with a laminating machine, the composite temperature is 70℃, the pressure is 0.3MPa, placed in a 60℃ oven for aging for 3 days, and the peel strength is examined. The test method is as follows:

[0154] Adhesion strength test: Refer to the national standard GB / T 8808, the test method for testing the peel strength of adhesive tapes.

[0155] Glue state: After preparing the glue, let it stand for 1 hour and observe with the naked eye.

[0156] Chemical resistance test: Soak the cured specimens in ethyl acetate at 60°C for 24 hours, take them out and place them in an environment of 25°C and 50% RH for 24 hours, observe the appearance of the adhesive layer and test the peel strength. The peel strength test standard is the same as before. If the adhesive layer has no obvious whitening and the force value remains above 85%, it is excellent; if the adhesive layer has obvious whitening or the force retention rate is 70%-85%, it is medium; if the adhesive layer bubbles / falls off or the force value is less than 70%, it is poor.

[0157] The measurement results are shown in Table 1.

[0158] Table 1

[0159]

[0160]

[0161] In Comparative Example 1, there is free monofunctional alcohol, and the viscosity of the base resin does not increase, while in Comparative Example 2, branching is serious and the polyester resin intermediate is easily cross-linked; due to the steric effect, the viscosity of the polyester resin intermediate in Comparative Example 4 is difficult to increase; and the adhesives obtained in Comparative Examples 3, 5, 6, and 7 have poor bonding effects.

[0162] It can be seen from the above examples and comparative examples that the acrylate-modified polyester resin obtained in the present invention has excellent bonding properties to non-polar substrates such as PP or PE.

[0163] It should be understood that the above embodiments are exemplary and are not intended to encompass all possible implementations of the claims. Various modifications and variations may be made to the above embodiments without departing from the scope of this disclosure. Similarly, the various technical features of the above embodiments may be arbitrarily combined to form additional embodiments of the present invention that may not be explicitly described. Therefore, the above embodiments merely illustrate several implementations of the present invention and do not limit the scope of protection of the patent of this invention.

Claims

1. A method for preparing an acrylate-modified polyester resin, characterized in that: The method comprises the following steps: (1) An acid anhydride with multiple functional groups reacts with a long-chain unsaturated monofunctional alcohol to produce an unsaturated intermediate; (2) subjecting the unsaturated intermediate obtained in step (1) to an esterification reaction with a dibasic acid and a diol, and then subjecting the resultant to a polycondensation reaction to obtain a polyester resin intermediate containing an unsaturated double bond; (3) subjecting the polyester resin intermediate containing unsaturated double bonds obtained in step (2) to a free radical polymerization reaction with an acrylate monomer to obtain the acrylate-modified polyester resin; Wherein, the acid anhydride having multiple functional groups is selected from trimellitic anhydride and / or pyromellitic dianhydride; The long-chain unsaturated monofunctional alcohol is selected from the compound represented by formula (I): Wherein, R1 is an alkane chain segment having more than 6 carbon atoms.

2. The preparation method according to claim 1, characterized in that R1 is an alkane segment having 6 to 22 carbon atoms, preferably an alkane segment having 6 to 12 carbon atoms; Preferably, the long-chain unsaturated monofunctional alcohol is selected from one or more of 8-nonen-1-ol, 9-decen-1-ol, 10-undecen-1-ol and 11-dodecen-1-ol.

3. The preparation method according to claim 1, characterized in that: In step (1), the molar ratio of the anhydride groups in the acid anhydride having multiple functional groups to the hydroxyl groups in the long-chain unsaturated monofunctional alcohol is 1 to 1.1:

1.

4. The preparation method according to claim 1, characterized in that In step (3), the acrylate monomer is selected from the compound represented by formula (II): wherein R2 is selected from hydrogen and C 1～6 Alkyl; R3 is a straight or branched alkane chain segment having more than 10 carbon atoms.

5. The preparation method according to claim 4, characterized in that: R2 is selected from hydrogen and C 1～3 The alkyl group is preferably hydrogen or methyl; The R3 is a straight chain or branched alkane segment having 10 to 30 carbon atoms, preferably a straight chain or branched alkane segment having 10 to 22 carbon atoms; Preferably, the acrylate monomer is selected from one or more of isodecyl acrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate and behenyl acrylate.

6. The preparation method according to claim 1, characterized in that The feeding molar ratio of the acrylic acid ester monomer to the long-chain unsaturated monofunctional alcohol is 0.6-0.8:

1.

7. The preparation method according to claim 1, characterized in that: In step (2), the molar ratio of the long-chain unsaturated monofunctional alcohol to the dibasic acid is 0.5 to 0.8:1; Preferably, the molar ratio of the diol: the dibasic acid and the acid anhydride having multiple functional groups is 1.3 to 2.0:

1.

8. The preparation method according to any one of claims 1 to 7, characterized in that The dibasic acid is selected from one or more of terephthalic acid, isophthalic acid, adipic acid, sebacic acid and dimer acid; Preferably, the diol is selected from one or more of ethylene glycol, butanediol, 2-methyl-1,3-propanediol and hexanediol.

9. An acrylate-modified polyester resin obtained according to the preparation method according to any one of claims 1 to 8.

10. Use of the acrylate-modified polyester resin obtained by the preparation method according to any one of claims 1 to 8 or the acrylate-modified polyester resin according to claim 9 in a non-polar substrate.

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