Preparation method of degradable polymer and application of degradable polymer in packaging

Abstract

The invention relates to the technical field of degradable polymers, in particular to a preparation method of a degradable polymer and application of the degradable polymer in packaging. Comprising the following raw materials in percentage by mass: 32-45% of a resin main body, 22-35% of modified poly (butylene succinate), 1-3% of a curing agent, 1.2-2% of an active polymer, 0.3-0.5% of a high-temperature tackifying adhesive protecting agent, 0.5-1.5% of an initiator, 2-5% of a plasticizer, 4-8% of a cross-linking agent and the balance of water, the modified poly (butylene succinate) is prepared by adopting a direct esterification-polycondensation process. The prepared degradable polymer poly (butylene succinate) is widely applied to the field of food packaging, and the materials have good transparency and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of degradable polymers, and more particularly to a preparation method of degradable polymers and application thereof in packaging. Background Art

[0002] Polymer materials are widely used in many fields due to their excellent performance. While bringing convenience to people, they also bring serious environmental pollution problems. Therefore, the development and utilization of biodegradable polymers are receiving more and more attention.

[0003] Biodegradable polymers include polylactic acid (PLA), polybutylene adipate-terephthalate (PBAT), polybutylene succinate (PBS), polycaprolactone (PCL), polypropylene carbonate (PPC), etc. Among them, polybutylene succinate (PBS) has attracted much attention due to its excellent mechanical properties and thermal stability, and has broad application prospects in packaging and film fields. However, due to its aliphatic structure, it has small intermolecular forces and low melt strength, and due to the regularity and flexibility of the PBS chain segment, it has high crystallinity and poor processing performance. Therefore, there have been almost no reports on its application in the fiber field at home and abroad in recent years. Generally speaking, the melt strength of a polymer can be improved by increasing the relative molecular mass, but increasing the relative molecular mass will also lead to problems such as high melt viscosity and poor flow properties.

[0004] How to develop PBS with large relative molecular weight, good melt flow properties and high melt strength, and to achieve good spinning and post-processing properties by regulating its crystallization properties, is the key point and difficulty to break through its application in the fiber field. Summary of the invention

[0005] The invention provides a preparation method of a degradable polymer and application thereof in packaging. The prepared degradable polymer polybutylene succinate is widely used in the field of food packaging. These materials have good transparency and mechanical properties.

[0006] In a first aspect, the present invention provides a degradable polymer, comprising the following raw materials in percentage by mass: 32-45% of a resin main body, 22-35% of modified polybutylene succinate, 1-3% of a curing agent, 1.2-2% of an active polymer, 0.3-0.5% of a high-temperature tackifying and protecting adhesive, 0.5-1.5% of an initiator, 2-5% of a plasticizer, 4-8% of a cross-linking agent, and the balance being water;

[0007] The modified polybutylene succinate is prepared by direct esterification-polycondensation process.

[0008] Preferably, the raw materials include the following mass percentages: 38-45% resin body, 25-35% modified polybutylene succinate, 2-3% curing agent, 1.5-2% active polymer, 0.4-0.5% high temperature adhesion promoter, 0.9-1.5% initiator, 3-5% plasticizer, 5-8% crosslinking agent, and the balance is water.

[0009] Preferably, the raw materials include the following mass percentages: 32-35% resin body, 30-32% modified polybutylene succinate, 2-3% curing agent, 1.8-2% active polymer, 0.4-0.5% high temperature adhesion promoter, 1.2-1.5% initiator, 4-5% plasticizer, 7-8% crosslinking agent, and the balance is water.

[0010] Preferably, the raw materials include the following mass percentages: 36% resin body, 32% modified polybutylene succinate, 2% curing agent, 1.5% active polymer, 0.4% high temperature adhesion promoter, 1.2% initiator, 4% plasticizer, 5% cross-linking agent, and the balance is water.

[0011] Preferably, the modified polybutylene succinate comprises 1,4-butanediol, 1,4-succinic acid, triphenyl phosphate, phenol, tetrachloroethane, glycerol, pentaerythritol and tetrabutyl titanate, and the mass ratio of glycerol to pentaerythritol is 1-3:2-5.

[0012] Preferably, the preparation method of modified polybutylene succinate is as follows: an esterification-polycondensation method is used to carry out a polymerization reaction in a high-pressure reactor. First, 1,4-butanediol and 1,4-butanediol are added to a polymerization reactor to synthesize polybutylene succinate, and a branching agent propylene glycol or pentaerythritol is added at 150-165° C. for 1-2 hours of esterification reaction; after the esterification is completed, a catalyst tetrabutyl titanate and a stabilizer triphenyl phosphate are added to carry out a condensation reaction, and the temperature is maintained at 200-240° C. After the stirring is completed, the modified polybutylene succinate is obtained.

[0013] Preferably, the main resin is one or more of epoxy acrylate resin, unsaturated polyester resin, urea-formaldehyde resin, vinyl ester resin, phenolic resin, bismaleimide resin, and cyanate ester resin.

[0014] Preferably, the curing agent is one or more of ammonium chloride, methyltetrahydrophthalic anhydride, hexamethylenetetramine, and diammonium hydrogen phosphate.

[0015] Preferably, the high temperature adhesion-enhancing adhesive protecting agent is a silane-modified polyether resin; and the initiator is sodium sulfite.

[0016] Preferably, the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, tricresyl phosphate, triphenyl phosphate, chlorinated paraffin, petroleum ester, alkyl sulfonate cresyl ester, polyethylene glycol, tri(2-ethylhexyl) trimellitate, and tri-n-butyl citrate.

[0017] Preferably, the crosslinking agent is one or more of maleic anhydride, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, triallyl isocyanurate, triallyl isocyanurate, and diethylene glycol dimethacrylate.

[0018] In a second aspect, the present invention provides a method for preparing a degradable polymer, comprising the following steps:

[0019] (1) adding the resin body into water and stirring to make it evenly dispersed to obtain a mixed solution A;

[0020] (2) adding modified polybutylene succinate to mixed solution A and stirring until the mixture is uniformly dispersed to obtain mixed solution B;

[0021] (3) Add the curing agent, active polymer, high temperature tackifier and initiator to mixed solution B, introduce nitrogen, stir until evenly dispersed, let stand, and then add to mixed solution C;

[0022] (4) Add the plasticizer and the cross-linking agent to the mixed solution C, stir evenly, and obtain a degradable polymer.

[0023] In a third aspect, the present invention provides an application of a degradable polymer, wherein the degradable polymer is applied in packaging manufacturing.

[0024] In summary, the present invention has the following beneficial effects:

[0025] 1. The present invention uses trifunctional propylene glycol and tetrafunctional pentaerythritol as branching agents, and adopts direct esterification-polycondensation process to prepare modified polybutylene succinate, which exhibits good thermal properties and flow properties, and is a class of biodegradable polymers with industrial promotion value;

[0026] 2. The present invention uses a variety of resins for compounding as the main body. Epoxy acrylate resin has the advantages of strong adhesion, high strength, low curing shrinkage, corrosion resistance, low toxicity, etc., but has the disadvantages of high brittleness and slow curing; phenolic resin has a short curing time, but low strength after curing and severe shrinkage; urea-formaldehyde resin is cheap, has sufficient raw materials, and contains polar oxygen atoms in its molecular structure, so it has good adhesion to the surface and is easy to combine with the stratum surface, but it has the disadvantages of poor weather resistance, poor initial adhesion, large shrinkage, large brittleness, water resistance, easy aging, etc. Unsaturated polyester resin has good performance after curing, but its heat resistance is insufficient. Thermosetting polyimide resin has excellent heat resistance. The advantages and disadvantages of several thermosetting resins are comprehensively considered and several resins are compounded in a certain proportion to retain their respective advantages to a certain extent;

[0027] 3. The preparation method of the degradable polymer of the present invention is simple and easy to operate, and is suitable for application in actual production and packaging manufacturing.

[0028] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to limit the scope of protection of the present invention. DETAILED DESCRIPTION

[0029] The present invention is further described in detail below in conjunction with the examples. It is particularly noted that if no specific conditions are specified in the following examples, the reactions are carried out according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following examples can be obtained from common commercial sources.

[0030] Preparation Example

[0031] Preparation Example 1

[0032] The modified polybutylene succinate includes 21 parts of 1,4-butanediol, 12 parts of 1,4-succinic acid, 8 parts of triphenyl phosphate, 15 parts of phenol, 12 parts of tetrachloroethane, propylene glycol, pentaerythritol and 31 parts of tetrabutyl titanate, and the mass ratio of propylene glycol to pentaerythritol is 1:2.

[0033] The preparation method of modified polybutylene succinate is as follows: an esterification-polycondensation method is adopted to carry out a polymerization reaction in a high-pressure reactor, firstly, 1,4-butanediol and 1,4-butanediol are added into a polymerization reactor to synthesize polybutylene succinate, and a branching agent propylene glycol or pentaerythritol is added at the same time, and an esterification reaction is carried out at 165° C. for 2 hours; after the esterification is completed, a catalyst tetrabutyl titanate and a stabilizer triphenyl phosphate are added to carry out a condensation reaction, and the temperature is maintained at 240° C. After the stirring is completed, the modified polybutylene succinate is obtained.

[0034] Preparation Example 2

[0035] The modified polybutylene succinate includes 25 parts of 1,4-butanediol, 15 parts of 1,4-succinic acid, 10 parts of triphenyl phosphate, 18 parts of phenol, 14 parts of tetrachloroethane, propylene glycol, pentaerythritol and 28 parts of tetrabutyl titanate, and the mass ratio of propylene glycol to pentaerythritol is 1:3.

[0036] The preparation method of modified polybutylene succinate is as follows: an esterification-polycondensation method is used to carry out a polymerization reaction in a high-pressure reactor, firstly, 1,4-butanediol and 1,4-butanediol are added into a polymerization reactor to synthesize polybutylene succinate, and a branching agent propylene glycol or pentaerythritol is added at the same time, and an esterification reaction is carried out at 165° C. for 1.5 hours; after the esterification is completed, a catalyst tetrabutyl titanate and a stabilizer triphenyl phosphate are added to carry out a condensation reaction, and the temperature is maintained at 240° C. After the stirring is completed, the modified polybutylene succinate is obtained.

[0037] Preparation Example 3

[0038] The modified polybutylene succinate includes 16 parts of 1,4-butanediol, 6 parts of 1,4-succinic acid, 5 parts of triphenyl phosphate, 10 parts of phenol, 8 parts of tetrachloroethane, propylene glycol, pentaerythritol and 20 parts of tetrabutyl titanate, and the mass ratio of propylene glycol to pentaerythritol is 1:5.

[0039] The preparation method of modified polybutylene succinate is as follows: an esterification-polycondensation method is adopted to carry out a polymerization reaction in a high-pressure reactor, firstly, 1,4-butanediol and 1,4-butanediol are added into a polymerization reactor to synthesize polybutylene succinate, and a branching agent propylene glycol or pentaerythritol is added at the same time, and an esterification reaction is carried out at 150° C. for 2 hours; after the esterification is completed, a catalyst tetrabutyl titanate and a stabilizer triphenyl phosphate are added to carry out a condensation reaction, and the temperature is maintained at 240° C. After the stirring is completed, the modified polybutylene succinate is obtained.

[0040] Example

[0041] Example 1

[0042] A degradable polymer comprises the following raw materials in percentage by mass: 32% of a resin main body, 22% of modified polybutylene succinate, 1% of a curing agent, 1.2% of an active polymer, 0.3% of a high-temperature adhesion-enhancing adhesive, 0.5% of an initiator, 2% of a plasticizer, 4% of a cross-linking agent, and the balance being water;

[0043] The modified polybutylene succinate is prepared in Preparation Example 1; the main resin is epoxy acrylate resin; the curing agent is ammonium chloride; the high-temperature adhesion-enhancing adhesive is silane-modified polyether resin STP-E15; the plasticizer is dioctyl phthalate; and the cross-linking agent is maleic anhydride;

[0044] A method for preparing a degradable polymer comprises the following steps:

[0045] (1) adding the resin body into water and stirring to make it evenly dispersed to obtain a mixed solution A;

[0046] (2) adding modified polybutylene succinate to mixed solution A and stirring until the mixture is uniformly dispersed to obtain mixed solution B;

[0047] (3) Add the curing agent, active polymer, high temperature tackifier and initiator to mixed solution B, introduce nitrogen, stir until evenly dispersed, let stand, and then add to mixed solution C;

[0048] (4) Add the plasticizer and the cross-linking agent to the mixed solution C, stir evenly, and obtain a degradable polymer.

[0049] Example 2

[0050] A degradable polymer comprises the following raw materials in percentage by mass: 38% of a resin main body, 27% of modified polybutylene succinate, 2% of a curing agent, 1.5% of an active polymer, 0.4% of a high-temperature adhesion-enhancing adhesive, 1.2% of an initiator, 3% of a plasticizer, 5% of a cross-linking agent, and the balance being water;

[0051] The modified polybutylene succinate is prepared in Preparation Example 2; the main resin is epoxy acrylate resin; the curing agent is ammonium chloride; the high-temperature adhesion-enhancing adhesive is silane-modified polyether resin STP-E15; the plasticizer is dioctyl phthalate; and the cross-linking agent is maleic anhydride;

[0052] A method for preparing a degradable polymer comprises the following steps:

[0053] (1) adding the resin body into water and stirring to make it evenly dispersed to obtain a mixed solution A;

[0054] (2) adding modified polybutylene succinate to mixed solution A and stirring until the mixture is uniformly dispersed to obtain mixed solution B;

[0055] (3) Add the curing agent, active polymer, high temperature tackifier and initiator to mixed solution B, introduce nitrogen, stir until evenly dispersed, let stand, and then add to mixed solution C;

[0056] (4) Add the plasticizer and the cross-linking agent to the mixed solution C, stir evenly, and obtain a degradable polymer.

[0057] Example 3

[0058] A degradable polymer comprises the following raw materials in percentage by mass: 40% of a resin main body, 30% of modified polybutylene succinate, 2% of a curing agent, 1.5% of an active polymer, 0.4% of a high-temperature adhesion-enhancing adhesive, 1.1% of an initiator, 3% of a plasticizer, 5% of a cross-linking agent, and the balance being water;

[0059] The modified polybutylene succinate was prepared in Preparation Example 3; the main resin was epoxy acrylate resin; the curing agent was ammonium chloride; the high temperature adhesion enhancing and protective adhesive was silane modified polyether resin STP-E15; the plasticizer was dioctyl phthalate; and the crosslinking agent was maleic anhydride;

[0060] A method for preparing a degradable polymer comprises the following steps:

[0061] (1) adding the resin body into water and stirring to make it evenly dispersed to obtain a mixed solution A;

[0062] (2) adding modified polybutylene succinate to mixed solution A and stirring until the mixture is uniformly dispersed to obtain mixed solution B;

[0063] (3) Add the curing agent, active polymer, high temperature tackifier and initiator to mixed solution B, introduce nitrogen, stir until evenly dispersed, let stand, and then add to mixed solution C;

[0064] (4) Add the plasticizer and the cross-linking agent to the mixed solution C, stir evenly, and obtain a degradable polymer.

[0065] Example 4

[0066] A degradable polymer comprises the following raw materials in percentage by mass: 45% of a resin main body, 35% of modified polybutylene succinate, 3% of a curing agent, 2% of an active polymer, 0.5% of a high-temperature adhesion-enhancing adhesive, 1.5% of an initiator, 5% of a plasticizer, 8% of a cross-linking agent, and the balance being water;

[0067] The modified polybutylene succinate is prepared in Preparation Example 2; the main resin is epoxy acrylate resin; the curing agent is ammonium chloride; the high-temperature adhesion-enhancing adhesive is silane-modified polyether resin STP-E15; the plasticizer is dioctyl phthalate; and the cross-linking agent is maleic anhydride;

[0068] A method for preparing a degradable polymer comprises the following steps:

[0069] (1) adding the resin body into water and stirring to make it evenly dispersed to obtain a mixed solution A;

[0070] (2) adding modified polybutylene succinate to mixed solution A and stirring until the mixture is uniformly dispersed to obtain mixed solution B;

[0071] (3) Add the curing agent, active polymer, high temperature tackifier and initiator to mixed solution B, introduce nitrogen, stir until evenly dispersed, let stand, and then add to mixed solution C;

[0072] (4) Add the plasticizer and the cross-linking agent to the mixed solution C, stir evenly, and obtain a degradable polymer.

[0073] Comparative Example

[0074] Comparative Example 1

[0075] The degradable polymer was prepared according to the method of Example 2, except that modified polybutylene succinate was not added.

[0076] Comparative Example 2

[0077] The degradable polymer was prepared according to the method of Example 2, except that no resin main body was added.

[0078] Performance Testing

[0079] Degradable performance test: 600mL of 65% mass fraction of degradable resin plugging agent aqueous solution was evenly added into 6 cylindrical heat-resistant molds, put into a high-temperature aging furnace and rolled and heated at 200℃ for 24h until completely solidified, then the solidified body was taken out, and the respective masses M1, M2, M3, M4, M5, M6, and M7 were weighed and recorded, and then put back into the mold, and continued to be put into a high-temperature aging furnace and rolled and heated at 200℃. It was taken out after 3d, 7d, 10d, 15d, 20d, and 30d respectively, and the solid part was taken out and weighed. The masses were recorded as M1', M2', M3', M4', M5', M6', and M7' respectively, and the respective degradation rates (x = (1-Mn') / Mn×100%) were calculated.

[0080] Table 1 Degradability test results

[0081]

[0082] It can be seen from Table 1 that, by comparing Examples 1, 2, 3, and 4, the greater the mass ratio of the modified polybutylene succinate added, the higher the degradation rate; and it can be seen from Comparative Example 1 that, when the modified polybutylene succinate is not added, the degradable properties of the material are greatly affected.

[0083] The above is only an exemplary embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A degradable polymer, characterized in that: The raw materials include the following mass percentages: 32-45% of resin body, 22-35% of modified polybutylene succinate, 1-3% of curing agent, 1.2-2% of active polymer, 0.3-0.5% of high temperature adhesion enhancing and protective adhesive, 0.5-1.5% of initiator, 2-5% of plasticizer, 4-8% of cross-linking agent, and the balance of water; The modified polybutylene succinate is prepared by direct esterification-polycondensation process.

2. The degradable polymer according to claim 1, characterized in that: The modified polybutylene succinate comprises 1, 4-butanediol, 1, 4-succinic acid, triphenyl phosphate, phenol, tetrachloroethane, propylene glycol, pentaerythritol and tetrabutyl titanate, and the mass ratio of propylene glycol to pentaerythritol is 1-3:2-5.

3. The degradable polymer according to claim 1, characterized in that: The preparation method of modified polybutylene succinate is as follows: an esterification-polycondensation method is used to carry out a polymerization reaction in a high-pressure reactor. First, 1, 4-butanediol and 1, 4-butanediol are added to the polymerization reactor to synthesize polybutylene succinate, and a branching agent propylene glycol or pentaerythritol is added at 150-165°C for 1-2h of esterification reaction. After the esterification is completed, a catalyst tetrabutyl titanate and a stabilizer triphenyl phosphate are added to carry out a condensation reaction, and the temperature is maintained at 200-240°C. After the stirring is completed, the modified polybutylene succinate is obtained.

4. The degradable polymer according to claim 1, characterized in that: The main resin is one or more of epoxy acrylate resin, unsaturated polyester resin, urea-formaldehyde resin, vinyl ester resin, phenolic resin, bismaleimide resin and cyanate ester resin.

5. The degradable polymer according to claim 1, characterized in that: The curing agent is one or more of ammonium chloride, methyltetrahydrophthalic anhydride, hexamethylenetetramine, and diammonium hydrogen phosphate.

6. The degradable polymer according to claim 1, characterized in that: The high temperature adhesion enhancing and protective adhesive is a silane-modified polyether resin; the initiator is sodium sulfite.

7. The degradable polymer according to claim 1, characterized in that: The plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, tricresyl phosphate, triphenyl phosphate, chlorinated paraffin, petroleum ester, alkyl sulfonate cresyl ester, polyethylene glycol, tri(2-ethylhexyl) trimellitate, and tri-n-butyl citrate.

8. The degradable polymer according to claim 1, characterized in that: The crosslinking agent is one or more of maleic anhydride, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, triallyl isocyanurate, triallyl isocyanurate, and diethylene glycol dimethacrylate.

9. The method for preparing a degradable polymer according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Add the resin body into water and stir to make it evenly dispersed to obtain a mixed solution A; (2) adding modified polybutylene succinate to mixed solution A and stirring until the mixture is evenly dispersed to obtain mixed solution B; (3) Add curing agent, active polymer, high temperature adhesion promoter and initiator to mixed liquid B, introduce nitrogen, stir until evenly dispersed, let stand, and then add to mixed liquid C; (4) Add the plasticizer and the cross-linking agent to the mixed solution C and stir evenly to obtain a degradable polymer.

10. An application of a degradable polymer, characterized in that: The degradable polymer according to any one of claims 1 to 8 is used in packaging manufacturing.

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