PHA lamination material and preparation method thereof

Abstract

The invention provides a PHA laminating material and a preparation method thereof, and the PHA laminating material comprises the following raw material components in parts by weight: 65-120 parts of a blend of crystalline PHA and amorphous PHA, 0.1-2 parts of a heat stabilizer, 0.1-2 parts of an antioxidant, 0.2-2 parts of a melt enhancer, 0.2-2 parts of a nucleating agent and 0-2 parts of a surfactant. By optimizing the raw material formula of the PHA lamination material, the problems of unstable melt pressure, film leakage and roller adhesion in the lamination process are effectively solved, the balance between the adhesion and separation of film paper is effectively adjusted, the adhesion and pulp return rate of the film and the paper are improved, and the PHA lamination material has excellent market application prospects.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite materials, and particularly relates to a PHA laminated film material and a preparation method thereof. BACKGROUND

[0002] At present, degradable material polylactic acid (PLA) has become a research hotspot of laminated films, but PLA can only be degraded under industrial composting conditions. As a new emerging material, polyhydroxyalkanoate (PHA) is a pure biological source and 100% degradable. Compared with other degradable materials such as PLA, polybutylene succinate (PBS), polybutylene adipate / terephthalate (PBAT) and polypropylene carbonate (PPC), the production, purification and application process of PHA is more green and biologically friendly, does not need petroleum-based industrial products as a synthetic source, and has lower degradation environment requirements and can achieve natural degradation without composting. Paper-plastic composite materials made of PHA do not cause environmental pollution.

[0003] However, PHA material also has many shortcomings: ① narrow processing window, poor heat resistance, and thermal decomposition temperature close to melting temperature. The thermal decomposition is intense above 170℃, and close to the melting temperature (Tm=165℃). ② low crystallization rate, long post-crystallization period, and the product is prone to brittleness due to post-crystallization, and the PHA in viscous flow state is prone to sticking to the roller. ③ low melt strength, and the laminated film is prone to defects such as fracture and bubble during lamination, affecting the appearance and performance of the product. ④ high crystallinity of PHA, and the molecular chains are difficult to diffuse and entangle with each other, the surface tension is small, and the adhesion to paper is small, which is not conducive to the forming of laminated paper cups; ⑤ PHA is a hydrophobic substance, which makes it difficult to return to slurry.

[0004] Chinese application CN114960278A discloses a preparation method of a plant fiber laminated PHA oil-proof material, which comprises preparation of nano-cellulose, modification of nano-cellulose, modification of PHA, and blending and lamination of the modified nano-cellulose and PHA to prepare the PHA oil-proof material. Although the oil-proof PHA laminated material can be degraded on the basis of ensuring the performance of PHA through esterification of nano-cellulose and complex treatment of modified PHA, it still cannot well solve at least the following problems: 1. Poor adhesion of PHA film to paper, resulting in poor paper cup forming and edge seepage and leakage problems; 2. PHA laminated paper cannot meet the paper-plastic slurry return, greatly reducing its use value and environmental protection.

[0005] Therefore, the application is proposed. SUMMARY

[0006] The first object of the present application is to provide a PHA lamination material to solve the problems of unstable melt pressure, film leakage and sticking roller in the lamination process of the existing PHA lamination material.

[0007] Specifically, the PHA lamination material comprises the following components by weight parts: a blend of crystalline PHA and amorphous PHA 65-120 parts, thermal stabilizer 0.1-2 parts, antioxidant 0.1-2 parts, melt enhancer 0.2-2 parts, nucleating agent 0.2-2 parts, and surfactant 0-2 parts.

[0008] Preferably, the raw materials comprise the following components: a blend of crystalline PHA and amorphous PHA 80-100 parts, thermal stabilizer 0.2-1 part, antioxidant 0.2-1 part, melt enhancer 0.2-1 part, nucleating agent 0.2-1 part, and surfactant 0.2-1 part.

[0009] The present application selects a blend of crystalline PHA (high strength) and amorphous PHA (high toughness and high elasticity) as the main material, which can ensure that the main material has high strength and high toughness.

[0010] Preferably, the weight ratio of crystalline PHA to amorphous PHA in the blend of crystalline PHA and amorphous PHA is 40 / 60-95 / 5, and more preferably the weight ratio is 70 / 30-90 / 10.

[0011] In some embodiments provided by the present application, the blend of crystalline PHA and amorphous PHA comprises 60-95 parts of at least one crystalline PHA and 5-40 parts of at least one amorphous PHA; the ratio of the two is preferably 3-4:1; more preferably, the amount of the blend of crystalline PHA and amorphous PHA in the raw materials is 65-100 parts, and the suitable amount is 65 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, etc.

[0012] The PHA according to the present application includes but is not limited to one or more than two combinations of polyhydroxybutyrate (PHB), poly-3-hydroxybutyrate / 3-hydroxyvalerate (PHBV), poly-3-hydroxybutyrate / 3-hydroxyhexanoate (PHBHHx), poly-3-hydroxyoctanoate (PHO), poly-3-hydroxydecanoate (PHD), poly-3-hydroxydodecanoate (PHDD), and poly-3-hydroxybutyrate / 4-hydroxybutyrate copolymer (P34HB).

[0013] Preferably, the crystalline PHA is selected from one or more than two combinations of PHB, PHBV, PHBHHx, PHO, PHD, PHDD, and P34HB; and the amorphous PHA is selected from PHBHHx and / or P34HB.

[0014] As a preferred embodiment of the present application, the blend of the crystalline PHA and the amorphous PHA is obtained by physical blending of 3-4:1 of crystalline PHB and amorphous P34HB or PHBHHx, or 3-4:1 of crystalline PHBV and amorphous P34HB or PHBHHx, or 3-4:1 of crystalline PHBHHx and amorphous P34HB or PHBHHx, or 3-4:1 of crystalline P34HB and amorphous P34HB or PHBHHx, and the blend exhibits excellent film forming performance during the film casting process, forming a PHA-based film casting modified material with both strength and toughness.

[0015] In some embodiments of the present application, the PDI of the amorphous PHA is 1.5-3.0, for example 1.5-2.5, preferably 1.6-2.1, etc.

[0016] In some embodiments of the present application, the PDI of the PHBHHx is ≤3, more preferably the PDI is 1.6-2.0.

[0017] In some specific embodiments of the present application, the PDI of the PHBHHx is 1.6, 1.7, 1.8, 1.9 or 2.0.

[0018] In some embodiments of the present application, the PDI of the P34HB is ≤2.5, preferably the PDI is 1.6-2.1.

[0019] In some specific embodiments of the present application, the PDI of the P34HB is 1.6, 1.7, 1.8, 1.9, 2.0 or 2.1.

[0020] The PHA film material provided by the present application, the heat stabilizer is selected from one or more of zinc stearate, calcium stearate, calcium ricinoleate, phosphite, lead di-salt phthalate, epoxide, glycerol ester and zinc ricinoleate, preferably zinc stearate, which can effectively stabilize the state of the material system during the film casting process.

[0021] The PHA film material provided by the present application, the antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 1076, thioester (preferably antioxidant DLTDP, antioxidant DSTDP) and phosphite ester (preferably antioxidant 168), preferably a combination of two antioxidants, such as antioxidant 1010 + antioxidant 168 in a weight ratio of 1:2-1:1, antioxidant 1076 + antioxidant DLTDP in a weight ratio of 1:1-1:2, etc.

[0022] The nucleating agent comprises one or more than two combinations of boron nitride (BN), sorbitol, aromatic phosphate salt, sodium cinnamate, phosphate metal salt, phosphate alkali metal, and sorbitol benzylidene derivative.

[0023] The melt enhancer is selected from one or more than two combinations of Joncryl ADR-4368, BASF ADR4400, BASF ADR 4468, chain extender DX-5, chain extender 6901, chain extender MSA7200, and chain extender HER.

[0024] The PHA film material further comprises a wet dispersing agent, wherein the weight amount of the wet dispersing agent in the raw materials is 0-2 parts, preferably 0.1-1 parts, and more preferably 0.2-0.5 parts.

[0025] The wet dispersing agent is selected from one or more than two combinations of sulfonated oil, soap, pull-apart powder BX, soybean lecithin, thiol, hydrazine, thiol acetal, and polyoxyethylene alkyl ether.

[0026] The PHA film material of the present application can effectively adjust the balance between the adhesion and separation of the film and paper by adding appropriate amounts of surfactants and wet dispersing agents.

[0027] The PHA film material of the present application has a melt index of 2-8 g / 10 min.

[0028] The PHA film material of the present application effectively solves the problems of unstable melt pressure, film leakage, and sticking roller during the film coating process by optimizing the raw materials, effectively adjusts the balance between the adhesion and separation of the film and paper, and improves the adhesion of the film and paper and the back slurry rate.

[0029] The second object of the present application is to provide the application of the PHA film material in PHA film paper.

[0030] The third object of the present application is to provide a PHA laminated paper, as one of the technical solutions, the PHA laminated paper comprises a base paper and a PHA film, wherein the raw material for preparing the PHA film comprises a blend of crystalline PHA and amorphous PHA; the weight ratio of the crystalline PHA to the amorphous PHA in the blend of crystalline PHA and amorphous PHA is 40 / 60-95 / 5; preferably, the weight ratio is 70 / 30-90 / 10. The sizing rate of the laminated paper is not less than 75%, preferably not less than 80%, 85%, 90% or even 95%.

[0031] As a preferred technical solution, the raw material for preparing the PHA film comprises the following components: 65-100 parts of a blend of crystalline PHA and amorphous PHA, 0.1-2 parts of a thermal stabilizer, 0.1-2 parts of an antioxidant, 0.2-2 parts of a melt enhancer, 0.2-2 parts of a nucleating agent, and 0-2 parts of a surfactant.

[0032] More preferably, the raw material for preparing the PHA film comprises the following components: 80-100 parts of a blend of crystalline PHA and amorphous PHA, 0.2-1 part of a thermal stabilizer, 0.2-1 part of an antioxidant, 0.2-1 part of a melt enhancer, 0.2-1 part of a nucleating agent, and 0.2-1 part of a surfactant.

[0033] The blend of crystalline PHA and amorphous PHA comprises 60-95 parts of at least one crystalline PHA and 5-40 parts of at least one amorphous PHA.

[0034] Preferably, the PHA comprises one or a combination of two or more of PHB, PHBV, PHBHHx, PHO, PHD, PHDD, and P34HB; preferably, the crystalline PHA is selected from one or a combination of two or more of PHB, PHBV, PHBHHx, PHO, PHD, PHDD, and P34HB; and the amorphous PHA is selected from PHBHHx and / or P34HB.

[0035] Further preferably, the blend of crystalline PHA and amorphous PHA is physically blended from 3-4:1 of crystalline PHB and amorphous P34HB or PHBHHx, or 3-4:1 of crystalline PHBV and amorphous P34HB or PHBHHx, or 3-4:1 of crystalline PHBHHx and amorphous P34HB or PHBHHx, or 3-4:1 of crystalline P34HB and amorphous P34HB or PHBHHx, and the above blend particularly exhibits excellent film-forming performance in the laminating process, forming a PHA base laminated modified material with both strength and toughness.

[0036] In some embodiments of the present invention, the PDI of the amorphous PHA is 1.5 to 3.0, a suitable range is, for example, 1.5 to 2.5, preferably 1.6 to 2.1, etc.

[0037] In some embodiments of the present invention, the PDI of PHBHHx is ≤3, and more preferably the PDI is 1.6~2.0.

[0038] In some specific embodiments of the present invention, the PDI of PHBHHx is 1.6, 1.7, 1.8, 1.9 or 2.0.

[0039] In some embodiments of the present invention, the PDI of the P34HB is ≤2.5, and preferably the PDI is 1.6~2.1.

[0040] In some specific embodiments of the present invention, the PDI of the P34HB is 1.6, 1.7, 1.8, 1.9, 2.0 or 2.1.

[0041] The PHA coated paper provided by the present invention, as a second technical solution, includes a base paper and a PHA film, wherein the PHA film is made of the aforementioned PHA coating material.

[0042] The base paper can be any conventional paper in the art, such as white cardboard, grey board, coated paper, offset paper, corrugated paper, writing paper, kraft paper, newsprint, etc. In the embodiments of the present invention, white cardboard is used, and more preferably, the basis weight of the base paper is 20 g / m². 2 ~350g / m 2 .

[0043] Preferably, the basis weight of the PHA membrane is 5 g / m³. 2 ~30g / m 2 .

[0044] A fourth objective of this invention is to provide a method for preparing the above-mentioned PHA coating material, the method comprising the following steps: S1. Mix all raw materials thoroughly to obtain a raw material mixture; S2. The raw material mixture is added to an extruder and then melted, extruded, and granulated to obtain the final product.

[0045] In the preparation method provided by this invention, in step S2: Preferably, the extruder is a twin-screw extruder, with the following temperature settings for each section: feeding section 110~130℃, compression section 130~150℃, homogenization section 140~160℃, and die head 150~165℃.

[0046] It is worth noting that the temperature in each of the above segments is preferably increased gradually.

[0047] Preferably, the main machine speed is 180-220 rpm, and the feeding speed is 8-12 Hz.

[0048] Preferably, the twin-screw processing temperature is 120-160 DEG C, the screw speed is 150-300 rpm, and the air blowing temperature is 30-60 DEG C.

[0049] In step S2, the PHA film-coating special material is prepared by air-blowing a conveying belt.

[0050] The application also provides a preparation method of the PHA film-coated paper, which comprises the following steps: S1, uniformly mixing all raw materials to obtain a raw material mixture; S2, adding the raw material mixture into an extruder to melt, extrude and granulate to obtain a PHA film-coating special material; S3, adding the PHA film-coating special material into a film-coating extruder to perform film-coating on a base paper by using an extrusion die.

[0051] In the preparation method, in step S2: Preferably, the extruder is a twin-screw extruder, and the temperature settings of each section are as follows: the feeding section is 110-130 DEG C, the compression section is 130-150 DEG C, the homogenization section is 140-160 DEG C, and the die is 150-165 DEG C.

[0052] It is worth noting that the temperature of each section is preferably gradually increased.

[0053] Preferably, the main machine speed is 180-220 rpm, and the feeding speed is 8-12 Hz.

[0054] Preferably, the twin-screw processing temperature is 120-160 DEG C, the screw speed is 150-300 rpm, and the air blowing temperature is 30-60 DEG C.

[0055] In step S2, the PHA film-coating special material is prepared by air-blowing a conveying belt.

[0056] In the preparation method, in step S3: Preferably, the temperature settings of each section of the film-coating extruder are as follows: the feeding section is 150-170 DEG C, the compression section is 160-180 DEG C, the homogenization section is 160-180 DEG C, and the die is 170-180 DEG C.

[0057] It is worth noting that the temperature of each section is preferably gradually increased.

[0058] Preferably, the main machine speed is 15-25 rpm, the pump speed is 8-12 rpm, and the melt pressure is 5-8 MPa.

[0059] Preferably, the temperature of the traction roller 1 and the traction roller 2 is set to be between 50-100℃, and the extrusion die is arranged between the traction roller 1 and the traction roller 2, and the material flows out of the die to be compounded with the paper to produce the paper-plastic composite material.

[0060] The technical scheme of the present application has the following beneficial effects: 1. The adhesion of the PHA film to the paper is enhanced, and the peeling force is high; 2. The PHA film-coated paper can be recycled, and the recycling rate can reach >90%; 3. The adhesion of the PHA film to the paper and the recycling property of the PHA film-coated paper can be balanced by adjusting the modification formula; 4. The production process is simple, the cost is low, and the application prospect is broad. DETAILED DESCRIPTION

[0061] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme of the present application will be described clearly and completely in combination with the embodiments in the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0062] All raw materials involved in the following embodiments are known commercially available products, such as Joncryl ADR-4368 available from BASF (food grade), antioxidant 1010 available from Liyanlong Supply Chain Management Co., Ltd., antioxidant DLTDP available from Songyuan Baifu Chemical Industry (Tangshan) Co., Ltd., alkyl phenol polyether phosphate TXP-10 available from Haian Petroleum Chemical Plant of Jiangsu Province, and nucleating agent BN available from Liaoning Boda Technology Co., Ltd.

[0063] In the following embodiments, the base paper used in the preparation of the film-coated paper is a conventional white card paper.

[0064] Embodiment 1

[0065] The present embodiment provides a PHA film-coated material, which comprises 80 parts of PHB, 20 parts of amorphous P34HB (PDI is 1.8), 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTDP, and 0.5 parts of nucleating agent BN, in terms of mass fraction.

[0066] The present embodiment also provides a PHA film-coated material, a film-coated paper and a preparation method thereof. The preparation method specifically comprises: S1: 60 parts of PHB, 40 parts of P34HB, 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTP, and 0.5 parts of nucleating agent were weighed by mass fraction, and physically mixed by a high-speed mixer for 25 min.

[0067] S2: The mixed material was melt-extruded by a twin-screw extruder, and the temperature of each section was set as follows: 120°C for the feeding section, 140°C for the compression section, 150°C for the homogenization section, and 155°C for the die head. The main machine speed was 200 rpm, the feeding speed was 10 Hz, and the material was pelletized by a wind-blowing conveying belt to prepare the PHA lamination film material. Preferably, the twin-screw processing temperature was 150°C, the screw speed was 250 rpm, and the wind-blowing temperature was 45°C.

[0068] S3: The PHA lamination film material was added into a lamination extruder, and the temperature of each section was set as follows: 160°C for the feeding section, 170°C for the compression section, 170°C for the homogenization section, and 175°C for the die head. The main machine speed was 20 rpm, the pump speed was 10 rpm, the melt pressure was 6 MPa, the temperature of traction roller 1 and traction roller 2 was set as 70°C, and the extrusion die head was between the traction roller 1 and the traction roller 2. The material flowed out of the die head and was compounded with paper to prepare a paper-plastic composite material, i.e., a PHA lamination paper.

[0069] The embodiment also provides a method for calculating the pulp recovery rate of the lamination paper (the same below): specifically, the lamination paper is cut into pieces, and then the sample is dissociated, the paper pulp is homogenized, and finally the pulp recovery rate of the lamination paper is calculated.

[0070] Example 2

[0071] The embodiment provides a PHA lamination film material, which comprises, by mass fraction, 70 parts of PHB, 30 parts of amorphous P34HB (PDI is 1.7), 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTDP, and 0.5 parts of nucleating agent BN.

[0072] The embodiment also provides a PHA lamination film material, a lamination paper, and a preparation method thereof. The preparation method specifically comprises the following steps: S1: 80 parts of PHB, 20 parts of P34HB, 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTP, and 0.5 parts of nucleating agent were weighed by mass fraction, and physically mixed by a high-speed mixer for 20 min.

[0073] S2: melt-extrude the mixed material through a twin-screw extruder, set the temperature of each section as follows: 120°C for the feeding section, 140°C for the compression section, 150°C for the homogenization section, and 155°C for the die head, the main machine speed is 200 rpm, the feeding speed is 10 Hz, and the material is granulated by a wind-blowing conveying belt to obtain the PHA lamination film material. Preferably, the twin-screw processing temperature is 160°C, the screw speed is 150 rpm, and the wind-blowing temperature is 60°C.

[0074] S3: add the PHA lamination film material into a lamination extruder, set the temperature of each section as follows: 160°C for the feeding section, 170°C for the compression section, 170°C for the homogenization section, and 175°C for the die head, the main machine speed is 20 rpm, the pump speed is 10 rpm, the melt pressure is 6 MPa, the temperature of traction roller 1 and traction roller 2 is set as 50°C, and the extrusion die head is between the traction roller 1 and the traction roller 2. The material flows out of the die head and is compounded with paper to prepare a paper-plastic composite material, i.e., a PHA-laminated paper.

[0075] Example 3

[0076] The example provides a PHA lamination film material, which comprises, in mass parts, 80 parts of PHB, 20 parts of amorphous P34HB (PDI is 1.6), 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTDP, and 0.5 parts of nucleating agent BN.

[0077] The example also provides a PHA lamination film material and a lamination paper and a preparation method thereof. The preparation method specifically comprises the following steps: S1: take, in mass parts, 80 parts of PHB, 20 parts of P34HB, 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTDP, and 0.5 parts of nucleating agent, and physically mix them by a high-speed mixer for 30 min.

[0078] S2: melt-extrude the mixed material through a twin-screw extruder, set the temperature of each section as follows: 120°C for the feeding section, 140°C for the compression section, 150°C for the homogenization section, and 155°C for the die head, the main machine speed is 200 rpm, the feeding speed is 10 Hz, and the material is granulated by a wind-blowing conveying belt to obtain the PHA lamination film material. Preferably, the twin-screw processing temperature is 160°C, the screw speed is 150 rpm, and the wind-blowing temperature is 60°C.

[0079] S3: The PHA film material is added into the film extruder, and the temperature of each section is set as follows: feeding section 160°C, compression section 170°C, homogenization section 170°C, die 175°C, main machine speed 20 rpm, metering pump speed 10 rpm, melt pressure 6 MPa, the temperature of traction roller 1 and traction roller 2 is set as 100°C, and the extrusion die is between the traction roller 1 and the traction roller 2. The material flows out of the die and is compounded with paper to prepare a paper-plastic composite material, i.e. PHA film paper.

[0080] Example 4

[0081] The embodiment provides a PHA film material, which comprises, in mass parts, 90 parts of PHB, 10 parts of amorphous P34HB (PDI is 1.8), 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 part of antioxidant 1010, 0.2 parts of antioxidant DLTDP and 0.5 parts of nucleating agent BN.

[0082] The embodiment simultaneously provides a PHA film material, a film-coated paper and a preparation method of the film-coated paper. S1: 80 parts of PHB, 20 parts of P34HB, 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 part of antioxidant 1010, 0.2 parts of antioxidant DLTDP and 0.5 parts of nucleating agent are weighed in mass parts and physically mixed for 25 minutes by a high-speed mixer.

[0083] S2: The mixed material is melt-extruded by a double-screw extruder, and the temperature of each section is set as follows: feeding section 120°C, compression section 140°C, homogenization section 150°C and die 155°C, the main machine speed is 200 rpm, the feeding speed is 10 Hz, and the material is pelletized by a wind-blowing conveying belt to prepare the PHA film material. Preferably, the double-screw processing temperature is 130°C, the screw speed is 250 rpm, and the wind-blowing temperature is 50°C.

[0084] S3: The PHA film material is added into the film extruder, and the temperature of each section is set as follows: feeding section 160°C, compression section 170°C, homogenization section 170°C, die 175°C, main machine speed 20 rpm, metering pump speed 10 rpm, melt pressure 6 MPa, the temperature of traction roller 1 and traction roller 2 is set as 80°C, and the extrusion die is between the traction roller 1 and the traction roller 2. The material flows out of the die and is compounded with paper to prepare a paper-plastic composite material, i.e. PHA film paper.

[0085] The embodiment simultaneously provides a method for calculating the pulp recovery rate of the film-coated paper (the same below): specifically, the film-coated paper is cut into pieces, and then the sample is dissociated, the paper pulp is homogenized, and is screened, and finally the pulp recovery rate of the film-coated paper is calculated.

[0086] Example 5

[0087] The embodiment provides a PHA laminated film material, which comprises 80 parts of PHB, 20 parts of P34HB (PDI is 1.9), 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 part of antioxidant 1010, 0.2 parts of antioxidant DLTP, 0.5 parts of a nucleating agent and 0.2 parts of alkylphenol polyether phosphate (TXP-10) in terms of mass fraction.

[0088] The embodiment simultaneously provides a PHA laminated film material, a laminated film paper and a preparation method of the laminated film paper. S1: 80 parts of PHB, 20 parts of P34HB, 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 part of antioxidant 1010, 0.2 parts of antioxidant DLTP, 0.5 parts of a nucleating agent and 0.2 parts of alkylphenol polyether phosphate (TXP-10) are weighed in terms of mass fraction, and physical mixing is performed through a high-speed mixer for 20-30 min.

[0089] S2: the mixed material is melt-extruded through a double-screw extruder, the temperature of each section is set as follows: 120 DEG C for a feeding section, 140 DEG C for a compression section, 150 DEG C for a homogenization section and 155 DEG C for a die head, the rotation speed of a main machine is 200 rpm, the feeding speed is 10 Hz, and the material is granulated through a wind-blowing conveying belt to prepare the PHA laminated film material, preferably, the processing temperature of the double-screw extruder is 145 DEG C, the rotation speed of the screw is 220 rpm, and the wind-blowing temperature is 40 DEG C.

[0090] S3: the PHA laminated film material is added into a laminated film extruder, the temperature of each section is set as follows: 160 DEG C for a feeding section, 170 DEG C for a compression section, 170 DEG C for a homogenization section and 175 DEG C for a die head, the rotation speed of a main machine is 20 rpm, the rotation speed of a metering pump is 10 rpm, the melt pressure is 6 MPa, the temperature of traction roller 1 and traction roller 2 is set as 90 DEG C, and the extrusion die head is between the traction roller 1 and the traction roller 2. The material is prepared into a paper-plastic composite material, namely the PHA laminated film paper, after flowing out of the die head and being compounded with paper.

[0091] Embodiment 6

[0092] The embodiment provides a PHA laminated film material, which comprises 80 parts of PHB, 20 parts of P34HB (PDI is 2.0), 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 part of antioxidant 1010, 0.2 parts of antioxidant DLTP, 0.5 parts of a nucleating agent and 0.3 parts of polyethylene glycol octadecyl ether in terms of mass fraction.

[0093] The embodiment simultaneously provides a PHA laminated film material, a laminated film paper and a preparation method of the laminated film paper. S1: 80 parts of PHB, 20 parts of P34HB, 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTP, 0.5 parts of nucleating agent, 0.3 parts of polyethylene glycol octadecyl ether were weighed in mass fraction, and physical mixing was performed by a high-speed mixer for 20 min.

[0094] S2: The mixed material was melt-extruded by a twin-screw extruder, and the temperature of each section was set as follows: 120°C for the feeding section, 140°C for the compression section, 150°C for the homogenization section, and 155°C for the die; the main machine speed was 200 rpm, the feeding speed was 10 Hz, and the material was pelletized by a wind-blowing conveying belt to prepare a PHA lamination film material. Preferably, the twin-screw processing temperature was 120°C, the screw speed was 200 rpm, and the wind-blowing temperature was 40°C.

[0095] S3: The PHA lamination film material was added into a lamination extruder, and the temperature of each section was set as follows: 160°C for the feeding section, 170°C for the compression section, 170°C for the homogenization section, and 175°C for the die; the main machine speed was 20 rpm, the pump speed was 10 rpm, the melt pressure was 6 MPa, the temperature of traction roller 1 and traction roller 2 was set as 60°C, and the extrusion die was between the traction roller 1 and the traction roller 2. The material flowed out of the die and was compounded with paper to prepare a paper-plastic composite material, i.e., a PHA lamination paper.

[0096] Example 7

[0097] The example provides a PHA lamination film material, which comprises, in mass fraction, 80 parts of PHB, 20 parts of P34HB (PDI is 1.8), 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTP, 0.5 parts of nucleating agent, 0.2 parts of alkylphenol polyether phosphate (TXP-10), and 0.3 parts of polyethylene glycol octadecyl ether.

[0098] The example also provides a PHA lamination film material and a lamination paper and a preparation method thereof. The preparation method specifically comprises the following steps: S1: 80 parts of PHB, 20 parts of P34HB, 0.3 parts of zinc stearate, 0.4 parts of Joncryl ADR-4368, 0.1 parts of antioxidant 1010, 0.2 parts of antioxidant DLTP, 0.5 parts of nucleating agent, 0.2 parts of alkylphenol polyether phosphate (TXP-10), and 0.3 parts of polyethylene glycol octadecyl ether were weighed in mass fraction, and physical mixing was performed by a high-speed mixer for 30 min.

[0099] S2: melt-extruding the mixed material through a twin-screw extruder, with the temperature settings of each section being 120°C for the feeding section, 140°C for the compression section, 150°C for the homogenization section, and 155°C for the die head, the main machine rotating at 200 rpm, the feeding speed being 10 Hz, and the material being pelletized by a wind-blowing conveying belt, to obtain the PHA lamination film material, preferably, the twin-screw processing temperature being 160°C, the screw rotating at 300 rpm, and the wind-blowing temperature being 60°C.

[0100] S3: adding the PHA lamination film material into a lamination extruder, with the temperature settings of each section being 160°C for the feeding section, 170°C for the compression section, 170°C for the homogenization section, and 175°C for the die head, the main machine rotating at 20 rpm, the metering pump rotating at 10 rpm, the melt pressure being 6 MPa, the temperature settings of the traction roller 1 and the traction roller 2 being 90°C, and the extrusion die head being between the traction roller 1 and the traction roller 2. The material flows out of the die head and is compounded with paper to prepare a paper-plastic composite material, i.e., a PHA-laminated paper.

[0101] Example 8

[0102] This example provides a PHA lamination film material, which is different from Example 1 only in the formula, specifically, including 60 parts of PHB, 20 parts of amorphous PHBHHx (PDI being 1.8), 0.1 part of zinc stearate, 0.1 part of Joncryl ADR-4368, 0.1 part of antioxidant 1010, 0.1 part of antioxidant DLTDP, and 0.2 part of nucleating agent BN, by mass fraction.

[0103] Example 9

[0104] This example provides a PHA lamination film material, which is different from Example 1 only in the formula, specifically, including 80 parts of PHD, 40 parts of amorphous PHBHHx (PDI being 1.6), 1 part of zinc stearate, 1 part of Joncryl ADR-4368, 1 part of antioxidant 1010, 0.5 part of antioxidant DLTDP, and 1 part of nucleating agent BN, by mass fraction.

[0105] Example 10

[0106] This example provides a PHA lamination film material, which is different from Example 1 only in the formula, specifically, including 96 parts of PHB, 24 parts of amorphous PHBHHx (PDI being 1.9), 2 parts of zinc stearate, 2 parts of Joncryl ADR-4368, 1 part of antioxidant 1010, 1 part of antioxidant DLTDP, 2 parts of nucleating agent BN, and 0.3 part of polyethylene glycol octadecyl ether, by mass fraction.

[0107] Example 11

[0108] The embodiment provides a PHA laminated film material, and the difference from the embodiment 1 is only that the formula is different, specifically, the PHA laminated film material comprises 60 parts of PHBV, 20 parts of amorphous P34HB (PDI is 1.7), 0.5 parts of zinc stearate, 0.5 parts of Joncryl ADR-4368, 0.2 parts of antioxidant 1010, 0.3 parts of antioxidant DLTDP, 1 part of nucleating agent BN and 0.2 parts of alkyl phenol polyether phosphate (TXP-10) in mass fraction.

[0109] Test example 1

[0110] The test example provides performance indexes of the modified materials of the laminated films prepared by the application, and the detection results are shown in Table 1.

[0111] Table 1

[0112] The test example also provides performance indexes of the laminated films prepared by the application, and the detection results are shown in Table 2.

[0113] Table 2

[0114] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the application, and not to limit them; although the application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the application.

Claims

1. A PHA-coated film material, characterized in that, The raw materials include the following components by weight: a blend of crystalline PHA and amorphous PHA 65-120 parts, thermal stabilizer 0.1-2 parts, antioxidant 0.1-2 parts, melt enhancer 0.2-2 parts, nucleating agent 0.2-2 parts, and surfactant 0-2 parts.

2. The PHA film material according to claim 1, characterized in that, The weight ratio of the crystalline PHA to the amorphous PHA in the blend of crystalline PHA and amorphous PHA is 40 / 60-95 / 5, preferably the weight ratio is 70 / 30-90 / 10; And / or, the blend of crystalline PHA and amorphous PHA contains 60-95 parts of at least one crystalline PHA and 5-40 parts of at least one amorphous PHA.

3. The PHA film material according to claim 1 or 2, characterized in that, The PHA includes one or a combination of two or more of PHB, PHBV, PHBHHx, PHO, PHD, PHDD, and P34HB; Preferably, the crystalline PHA is selected from one or a combination of two or more of PHB, PHBV, PHBHHx, PHO, PHD, PHDD, and P34HB; and the amorphous PHA is selected from PHBHHx and / or P34HB.

4. The PHA film material according to any one of claims 1-3, wherein, The PDI of the amorphous PHA is 1.5-3.0; The PDI of the PHBHHx is ≤3, preferably the PDI is 1.6-2.0; The PDI of the P34HB is ≤2.5, preferably the PDI is 1.6-2.

1.

5. The PHA film material according to any one of claims 1 to 4, characterized in that, The thermal stabilizer is selected from one or several of zinc stearate, calcium stearate, calcium ricinoleate, phosphite, lead di-salt phthalate, epoxide, glycerol ester, and zinc ricinoleate; And / or, the antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 1076, thioester, and phosphite ester.

6. The PHA film material according to any one of claims 1 to 5, characterized in that, The nucleating agent includes one or a combination of two or more of boron nitride, sorbitol, TMC-306, aryl phosphate salt, sodium cinnamate, phosphate metal salt, phosphate alkali metal, and sorbitol benzylidene derivative; And / or, the melt enhancer is selected from one or a combination of two or more of Joncryl ADR-4368, BASF ADR 4400, BASF ADR 4468, chain extender DX-5, chain extender 6901, chain extender MSA7200, and chain extender HER.

7. The PHA film material according to any one of claims 1 to 6, characterized in that, The surfactant is selected from one or a combination of two or more of polyethylene glycol octadecyl ether, polysorbate, aromatic polyethylene oxide, sorbitan derivative, block copolymer of polyethylene oxide and polypropylene oxide, polyethylene glycol ether, polyvinyl alcohol, alkyl sulfate, alkyl phosphate, stearate, and alkyl phenol polyether phosphate.

8. The PHA film material according to any one of claims 1 to 7, characterized in that, The raw materials further include a wet dispersant; The wet dispersant is selected from one or a combination of two or more of sulfonated oil, soap, laopen powder BX, soybean lecithin, thiol, hydrazide, and thiol acetal, and polyoxyethylene alkyl ether.

9. Process for the preparation of the PHA film material according to any one of claims 1 to 8, characterized in that, The method includes the following steps: S1, mixing all the raw materials uniformly to obtain a raw material mixture; S2, the raw material mixture is added to the extruder for melting, extruding, and granulating to obtain the product.

10. The method of claim 9, wherein, In the step S2, the extruder is a double-screw extruder, and the temperature settings are as follows: 110-130℃ for the feeding section, 130-150℃ for the compression section, 140-160℃ for the homogenization section, and 150-165℃ for the die head. Preferably, the main machine rotation speed is 180-220 rpm, and the feeding speed is 8-12 Hz. More preferably, the double-screw processing temperature is 120-160℃, the screw rotation speed is 150-300 rpm, and the air blowing temperature is 30-60℃.

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