WO2016119557A1

WO2016119557A1 - Thermoplastic starch that can be heated repeatedly, and preparation method for same

Info

Publication number: WO2016119557A1
Application number: PCT/CN2015/099661
Authority: WO
Inventors: 陈庆; 曾军堂; 叶任海
Original assignee: 成都新柯力化工科技有限公司
Priority date: 2015-01-30
Filing date: 2015-12-30
Publication date: 2016-08-04
Also published as: CN104672507A; CN104672507B

Abstract

A thermoplastic starch that can be heated repeatedly is provided in the present invention. Said starch contains the following ingredients in the following parts by weight: 80-85 parts starch, 10-15 parts hydrogenated aliphatic dimer acid, 2-3 parts aminating agent, and 0.5-1.5 parts tackifying agent; by means of amination of the starch and polycondensation thereof with hydrogenated aliphatic dimer acid, the present invention overcomes the problem of the direct use of a small molecular plasticizer to plasticize starch resulting in said plasticizer being easily separated out and volatilized and lost; thus, the invention enables the thermoplastic starch to endure repeated high-temperature heating. A preparation method is further provided. In the method, a dual-stage, dual-screw reaction extruder is used to subject the starch to amorphization, polycondensation-thermoplasticization, and deep polycondensation on a continuous basis, ultimately changing the starch into a thermoplastic starch that can be heated repeatedly.

Description

Description: A thermoplastic starch which can be repeatedly processed by heat and its preparation method

[0001] The present invention relates to the field of deep processing of starch, and in particular to the thermoplastic treatment of starch. Thermoplastic starch can be used in biodegradable plastics, environmentally friendly hot melt adhesives and other products.

Background technique

[0002] Starch is an important renewable and biodegradable natural polymer material, which is widely used in food and textile industries. In order to further broaden the use of starch in the industrial field, the starch is desired to become a thermoplastic polymer material. However, there are a large number of hydroxyl groups on the starch molecule, and the adjacent molecules form strong crystals through hydrogen bonding, and a large number of molecular chains aggregate to form a close double helix structure, resulting in a hard shell of the starch crystal particles. The hydrogen bond interaction due to the large amount of hydroxyl groups on the surface of the starch granules has a strong intramolecular synergistic effect and is not easily plasticized. In addition, the melting point of natural starch is higher than the thermal decomposition temperature, resulting in poor hot workability. Therefore, starch cannot be subjected to high-temperature thermoplastic processing like plastic polymers.

[0003] The so-called thermoplastic is generally understood to be the ability of a material to be processed repeatedly without physical property changes and having thermal stability. Natural starch is a rigid substance with hydrogen bonds between molecules. It does not have thermoplasticity and cannot be melt-formed. There is no melting process when directly heated, and it decomposes above 30CTC. Therefore, coking and poor processing performance are likely to occur during the processing of starch plastics. It is more difficult to use. In order to make the starch thermoplastic, a small molecule plasticizer can be used, and a small molecule plasticizer is drilled between the macromolecular starch chains, so that the polar group of the plasticizer interacts with the polar group of the starch molecule instead of the starch molecule. The polar action causes the starch granules to swell and increase the intermolecular distance, thereby weakening the van der Waals force between the starch molecular chains, making the molecular chains easy to move, reducing the melting temperature of the starch, and making it easy to be hot processed.

[0004] There are many starch plasticizers currently studied, generally polar plasticizers, the main features of which are: polar groups capable of interacting with hydroxyl or ether bonds, such as: hydroxyl, amide, carboxyl, carbonyl Wait. Because small molecule plasticizers are more likely to penetrate into the interior of the starch crystals, swelling the starch molecules, thereby destroying their original structure and lowering the glass transition temperature, making them exhibit thermoplasticity.

[0005] Chinese Patent Application No. 200810110041. 0 discloses a thermoplastic starch plastic from starch, A plasticizer, maleic anhydride, etc., wherein the plasticizer uses a small molecule polar material such as glycerin or ethylene glycol.

[0006] Chinese Patent Application No. 201180055540. 4 discloses a thermoplastic starch composition comprising 40% to 96% starch, and 1% to 40% plasticizer. The plasticizer is a hydroxyl group organic compound, a hydroxy polymer plasticizer, a hydrogen bond organic compound, a fatty acid, and a mixture thereof.

[0007] Chinese Patent Application No. 201310754312. 7 discloses a low water content thermoplastic cassava modified starch and a preparation process thereof, and the raw materials including tapioca starch, plasticizer and initiator are placed in a stirred reaction kettle for grafting. reaction. Among them, the plasticizer is dioctyl phthalate, diisononyl phthalate, dioctyl sebacate, triphenyl phosphate, paraffin oil, chlorinated paraffin, eucalyptus oil, epoxidized soybean oil. A type of dipentaerythritol ester.

[0008] According to the above, in order to realize the thermoplastic processing of starch, a small molecule polar material is usually used as a plasticizer, and a plasticizer such as glycerin or ethylene glycol contains a hydroxyl group, an amino group, an amide group or the like in a small molecule. It can form a stronger hydrogen bond with the hydroxyl groups in the starch molecular chain, thereby destroying its original structure and lowering the glass transition temperature to make it exhibit thermoplasticity. On the one hand, the small molecule plasticizer has a significant reduction in hydrogen bonding to starch, and the plasticizing effect is excellent. On the other hand, the small molecule plasticizer will lower the molecular weight of the starch, resulting in a decrease in the mechanical properties of the starch, and a small molecule increase during hot working. Plasticizers are easily precipitated, volatilized, and lost. Therefore, starch is no longer thermoplastic when it is repeatedly subjected to hot processing, which is the main reason for the poor thermal stability of thermoplastic starch.

Summary of invention

technical problem

[0009] At present, thermoplastic starch contains a small molecule plasticizer, and small molecule plasticizer is easily precipitated and volatilized during thermal processing, which makes it difficult to repeatedly process thermoplastic starch at high temperatures.

Problem solution

Technical solution

[0010] The present invention provides a re-heat-processable thermoplastic starch which is obtained by amination of a starch with a hydrogenated aliphatic dimer acid, which can be repeatedly thermoplastic due to the absence of a small molecular weight plasticizer. machining. A method of preparing the thermoplastic starch is further provided.

[0011] In order to achieve the above object, the present invention adopts the following technical solutions:

[0012] A thermoplastic starch that can be repeatedly heat processed, characterized in that: starch is aminated, and hydrogenated with aliphatic The re-heat-processable thermoplastic starch formed by polycondensation of dimer acid comprises the following components by weight:

[0013] 80-85 parts of starch,

[0014] hydrogenated aliphatic dimer acid 10-15 parts,

[0015] Aminating agent 2-3 parts,

5-1. 5份, [0016]

[0017] wherein the starch is a mixture of one or more of tapioca starch, sweet potato starch, potato starch, banana starch, acorn starch, sago starch, konjac starch, pea starch, corn starch.

[0018] The hydrogenated aliphatic dimer acid is derived from dimerized linoleic acid, dimerized oleic acid, dipolylinolenic acid, dimerized soybean acid or dimerized oleic acid, and C ₁₈ derived from dimeric acid The dimer acid of the hydrogenated fatty acid, the dimer acid accounts for 70-80% of the total mass of the hydrogenated aliphatic dimer acid.

[0019] The aminating agent is at least one of hydroxylamine sulfate, hexamethylenediamine, decanediamine, and diethylhydroxylamine.

[0020] The tackifier processing aid is at least one of maleic rosin, rosin glyceride, hydrogenated rosin glyceride, pentaerythritol rosin ester, hydrogenated pentaerythritol rosin ester, and acrylic acid modified rosin.

[0021] A method for preparing a thermoplastic starch that can be repeatedly processed by heat, characterized in that the specific steps are as follows:

[0022] (1) 80-85 parts by weight of starch and 2-3 parts by weight of the aminating agent is refined by a grinder or a micro-machine to a powder particle size of 5 microns to obtain an aminated starch;

[0023] (2) The aminated starch obtained in the step (1) and 10-15 parts by weight of the hydrogenated aliphatic dimer acid are added to the high-speed mixer, the temperature of the high-speed mixer is raised to 100-120 ° C, and the stirring speed is controlled at 200-300 rpm, adding glacial acetic acid while stirring, pre-condensing in a high-speed mixer for 30-45 min, the amount of glacial acetic acid added is controlled to 2-3% of the mass of the hydrogenated aliphatic dimer acid;

[0024] (3) The pre-polycondensate obtained in the step (2) is added to the double-stage twin-screw reaction extruder, and the first-stage screw reactor temperature is set at 80-120 ° C, and the mixture is mixed with the gap between the screw and the barrel. , the crystal of the aminated starch is relaxed to form an amorphous gel powder, and polycondensed with a hydrogenated aliphatic dimer acid; through a second-stage screw reactor, the second-stage screw reactor temperature is 140_175 ° C, and the process is accompanied by deep polycondensation. For the generation of moisture and gas, a two-stage devolatilizer is provided, and the degassing vacuum is reduced to 0. 05-0. 08 MPa, and the thermoplastic starch which can be repeatedly heat-processed is obtained by continuous polycondensation, devolatilization, and extrusion dicing.

[0025] In the above preparation method, the grinding machine described in the step (1) selects a ball mill, and the micro-machine uses a vortex flow micro-machine, and the starch is refined by the crushing of the starch granules and the starch is rapidly passed through the fine interfacial reaction. Amination.

[0026] The above preparation method, the step (3) of the double-stage twin-screw reaction extruder comprises a first-order reactor and a second-order reactor, and the first-order and second-order reactors are closely linked, and only one feed port is provided. And a discharge port, wherein the first-order reactor is an anisotropic twin-screw reaction extruder, and the counter-rotating meshing thread element relaxes the crystal of the aminated starch to form an amorphous gel powder, and is polycondensed with the hydrogenated aliphatic dimer acid. The second-order reactor is a co-rotating twin-screw reaction extruder, and the co-rotating screw elements continuously deep-condense the aminated starch and the hydrogenated aliphatic dimer acid, and the generated water is generated by the two-stage vacuum devolatilizer And the gas is eliminated in time to achieve continuous polycondensation, devolatilization, and extrusion pelletizing.

[0027] The present invention relates to a re-heat-processable thermoplastic starch and a preparation method thereof, which are capable of polycondensation of a starch and a polycondensation of a hydrogenated aliphatic dimer acid, thereby overcoming the small molecule when directly plasticizing a starch using a small molecule plasticizer. The plasticizer is prone to precipitation and volatilization loss, and the thermoplastic starch is subjected to repeated hot working at high temperatures. The thermoplastic starch has good hot melt at 101. 8 ° C. When the temperature is raised to 200 ° C, the heat weight loss lines are substantially parallel, and no degradation, charring, decomposition occurs, and the hot workability is reproducible.

[0028] Further, in order to avoid hydrolysis during starch polycondensation and high temperature and shear degradation during polycondensation, a double-stage twin-screw reaction extruder is used to crystallize the aminated starch in the first-order reactor. Relaxation to form amorphous gel powder, polycondensation with hydrogenated aliphatic dimer acid, with certain thermoplasticity; continuous continuous condensation of aminated starch and hydrogenated aliphatic dimer acid through a second-order reactor; continuous starch amorphization Polycondensation Thermoplasticization, deep polycondensation, and finally the starch becomes a thermoplastic starch with reproducible hot workability. The thermoplastic starch can be used for biodegradable plastics, environmentally friendly hot melt adhesives, and the like.

[0029] The hot workability of a re-heat-processable thermoplastic starch of the present invention was tested, and the mixture was heated and stirred at 140 ° C for 3 times, and the melt viscosity and appearance did not change significantly, and the strength loss was small, and the hot workability was repeated. Good, performance is as follows:

[] [Table 1]

Advantageous effects of the invention

Beneficial effect

[0030] The present invention provides a re-heat-processable thermoplastic starch and a preparation method thereof, and the outstanding features and beneficial effects compared with the prior art are:

[0031] 1. The thermoplastic starch of the present invention is formed by polycondensation of a hydrogenated aliphatic dimer acid by amination of starch, and overcomes the problem that small molecule plasticizer is easily precipitated and volatilized when directly using a small molecule plasticizer to plasticize starch. Defects enable thermoplastic starch to achieve repeated thermal processing at elevated temperatures. The thermoplastic starch has good hot melt at 101. 8 ° C. When the temperature rises to 20 CTC, the heat weight loss line is substantially parallel, no degradation, scorch, decomposition occurs, and no coke occurs in three consecutive 20 minutes heating, Good reproducible hot workability.

[0032] 2. The thermoplastic starch of the present invention adopts a double-stage twin-screw reaction extruder, which successively makes the starch successively amorphous, polycondensation, thermoplasticization, deep polycondensation, avoids hydrolysis, and polycondensation during starch polycondensation. Defects in high temperature and shear degradation during the process.

[0033] 3. The preparation method of the thermoplastic starch of the invention has the advantages of simplified process, high reaction efficiency and continuous scale production. Brief description of the drawing

DRAWINGS

1 is a differential scanning calorimetry (DSC) chart of a thermoplastic starch of the present invention. Through testing, the thermoplastic starch has good hot melt at 101. 8 ° C, and the heat weight loss line is substantially parallel within 200 ° C, so the thermal workability is good.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1

[0036] (1) 40 parts by weight of tapioca starch, 40 parts by weight of pea starch and 2 parts by weight of hydroxylamine sulfate were refined by a ball mill to a powder particle size of 5 μm to obtain an aminated starch;

[0037] (2) adding the aminated starch obtained in the step (1) to 10 parts by weight of the dimerized linoleic acid and the dimer acid of the C ₁₈ hydrogenated fatty acid derived from the dipolyglycolic acid into a high-speed mixer, a high-speed mixer The temperature is raised to 100 ° C, the stirring speed is controlled at 200-300 rpm, while adding glacial acetic acid while stirring, pre-condensing 3 Omin in a high-speed mixer, the amount of glacial acetic acid added is controlled at 2% of the mass of the hydrogenated aliphatic dimer acid;

[0038] (3) The pre-polycondensate obtained in the step (2) is added to the double-stage twin-screw reaction extruder, and the first-stage screw reactor temperature is set to 80-120 ° C, and the mixture is mixed with the gap between the screw and the barrel. , the crystal of the aminated starch is relaxed to form an amorphous gel powder, and polycondensed with a hydrogenated aliphatic dimer acid; through a second-stage screw reactor, the second-stage screw reactor temperature is 140_175 ° C, and the process is accompanied by deep polycondensation. For the generation of moisture and gas, a two-stage devolatilizer is provided, and the degassing vacuum is reduced to 0. 05-0. 08 MPa, and the thermoplastic starch is obtained by continuous polycondensation, devolatilization, and extrusion dicing.

[0039] By performing a DSC test on the thermoplastic starch, see Figure 1. The thermoplastic starch has good hot melt at 101. 8 ° C, and the heat weight loss line is substantially parallel within 200 ° C, so that the hot workability is reproducible. Invention embodiment

Embodiments of the invention

Embodiment 2

(1) 40 parts by weight of sweet potato starch, 45 parts by weight of acorn starch and 3 parts by weight of hexamethylenediamine are refined by a vortex flow refiner to a powder particle size of 5 μm to obtain an aminated starch. ; [0042] (2) adding the aminated starch obtained in the step (1) and 15 parts by weight of dimerized oleic acid and the dimer acid of the C ₁₈ hydrogenated fatty acid derived from the dipolyglycolic acid to a high-speed mixer, high-speed mixer temperature Raise to 100 ° C, the stirring speed is controlled at 250 rpm, while adding glacial acetic acid while stirring, pre-condensing for 45 min in a high-speed mixer, the amount of glacial acetic acid added is controlled at 3% of the mass of the hydrogenated aliphatic dimer acid;

[0043] (3) The pre-polycondensate obtained in the step (2) is added to the double-stage twin-screw reaction extruder, and the first-stage screw reactor temperature is set at 80-120 ° C, and the mixture is mixed with the gap between the screw and the barrel. , the crystal of the aminated starch is relaxed to form an amorphous gel powder, and polycondensed with a hydrogenated aliphatic dimer acid; through a second-stage screw reactor, the second-stage screw reactor temperature is 140_175 ° C, and the process is accompanied by deep polycondensation. For the generation of moisture and gas, a two-stage devolatilizer is provided, and the degassing vacuum is reduced to 0. 05-0. 08 MPa, and the thermoplastic starch is obtained by continuous polycondensation, devolatilization, and extrusion dicing.

[0044] 60 parts of the thermoplastic starch obtained in Example 2 and 40 parts of polycaprolactone (PCL) were blown on a 45FM800 type film blowing machine at 125 ° C, and the film tensile strength was 21 MPa.

Embodiment 3

(1) 80 parts by weight of sago starch and 3 parts by weight of decyl diamine are refined by a grinder to a powder particle size

5 microns, obtaining aminated starch;

[0047] (2) the aminated starch obtained in the step (1) and 10 parts by weight of the dimeric linolenic acid and the dimer acid of the C ₁₈ hydrogenated fatty acid derived from the dipolyglycolic acid are added to a high-speed mixer, a high-speed mixer. The temperature is raised to 110 ° C, the stirring speed is controlled at 300 rpm, while stirring, glacial acetic acid is added, and the mixture is pre-condensed in a high-speed mixer for 35 m in, and the amount of glacial acetic acid is controlled to be 2% of the mass of the hydrogenated aliphatic dimer acid;

[0048] (3) The pre-polycondensate obtained in the step (2) is added to the double-stage twin-screw reaction extruder, and the first-stage screw reactor temperature is set at 80-120 ° C, and the mixture is mixed with the gap between the screw and the barrel. , the crystal of the aminated starch is relaxed to form an amorphous gel powder, and polycondensed with a hydrogenated aliphatic dimer acid; through a second-stage screw reactor, the second-stage screw reactor temperature is 140_175 ° C, and the process is accompanied by deep polycondensation. For the generation of moisture and gas, a two-stage devolatilizer is provided, and the degassing vacuum is reduced to 0. 05-0. 08 MPa, and the thermoplastic starch is obtained by continuous polycondensation, devolatilization, and extrusion dicing.

[0049] The thermoplastic starch obtained in Example 3 was blended with 60 parts of polyamide hot melt adhesive to prepare an environmentally friendly hot melt adhesive, which can be heated for a long time and repeatedly processed. The performance test is as follows:

[] [Table 2]

Embodiment 4

[0051] (1) 80 parts by weight of the starch starch and 2 parts by weight of diethylhydroxylamine are refined by a vortex flow machine to a powder particle size of 5 μm to obtain an aminated starch;

[0052] (2) adding the aminated starch obtained in the step (1) to 12 parts by weight of dimerized soybean oil and the dimer acid of the C ₁₈ hydrogenated fatty acid derived from the dimeric acid, and adding the high temperature mixer to the high speed mixer. To 120 ° C, the stirring speed is controlled at 300 rpm, while adding glacial acetic acid while stirring, pre-condensing for 45 min in a high-speed mixer, the amount of glacial acetic acid added is controlled at 2% of the mass of the hydrogenated aliphatic dimer acid;

[0053] (3) The pre-polycondensate obtained in the step (2) is added to the double-stage twin-screw reaction extruder, and the first-stage screw reactor is set at a temperature of 80-120 ° C, and is kneaded by the gap between the spiral rib and the barrel. , the crystal of the aminated starch is relaxed to form an amorphous gel powder, and polycondensed with a hydrogenated aliphatic dimer acid; through a second-stage screw reactor, the second-stage screw reactor temperature is 140_175 ° C, and the process is accompanied by deep polycondensation. For the generation of moisture and gas, a two-stage devolatilizer is provided, and the degassing vacuum is reduced to 0. 05-0. 08 MPa, and the thermoplastic starch is obtained by continuous polycondensation, devolatilization, and extrusion dicing.

Example 5

(1) 85 parts by weight of potato starch and 3 parts by weight of hydroxylamine sulfate are refined into a powder by a grinder 5 microns in diameter to obtain aminated starch;

[0056] (2) adding the aminated starch obtained in the step (1) to 15 parts by weight of dimerized acid and dimer acid of the C ₁₈ hydrogenated fatty acid derived from the dipolyglycolic acid to a high-speed mixer, high-speed mixer temperature Raise to 100 ° C, the stirring speed is controlled at 200 rpm, while adding glacial acetic acid while stirring, pre-condensing for 30 min in a high-speed mixer, the amount of glacial acetic acid added is controlled at 3% of the mass of the hydrogenated aliphatic dimer acid;

[0057] (3) The pre-polycondensate obtained in the step (2) is added to the double-stage twin-screw reaction extruder, and the first-stage screw reactor temperature is set at 80-120 ° C, and the mixture is mixed with the gap between the screw and the barrel. , the crystal of the aminated starch is relaxed to form an amorphous gel powder, and polycondensed with a hydrogenated aliphatic dimer acid; through a second-stage screw reactor, the second-stage screw reactor temperature is 140_175 ° C, and the process is accompanied by deep polycondensation. For the generation of moisture and gas, a two-stage devolatilizer is provided, and the degassing vacuum is reduced to 0. 05-0. 08 MPa, and the thermoplastic starch is obtained by continuous polycondensation, devolatilization, and extrusion dicing.

Industrial applicability

[0058] The invention relates to a re-heat-processable thermoplastic starch and a preparation method thereof, which can overcome the direct small-molecule plasticizer to plasticize starch by amidating starch and polycondensing with hydrogenated aliphatic dimer acid The plasticizer is prone to precipitation and volatilization loss, and the thermoplastic starch is subjected to repeated hot working at high temperatures. The thermoplastic starch has good hot melt at 101. 8 ° C. When the temperature is raised to 200 ° C, the heat weight loss lines are substantially parallel, and no degradation, charring, decomposition occurs, and the hot workability is reproducible.

Claims

Claim

[Claim 1] A re-heat-processable thermoplastic starch characterized by: a reductively heat-treatable thermoplastic starch formed by amination of a starch with a hydrogenated aliphatic dimer acid, comprising the following components by weight; :

80-85 parts of starch, 10-15 parts of hydrogenated aliphatic dimer acid,

Aminating agent 2-3 parts,

Additive processing aid 0. 5-1. 5 parts,

The starch is a mixture of one or more of tapioca starch, sweet potato starch, potato starch, banana starch, acorn starch, sago starch, konjac starch, pea starch, corn starch;

The hydrogenated aliphatic dimer acid is derived from dimerized linoleic acid, dimerized oleic acid, dimeric linolenic acid, dimerized soybean acid or dimerized oleic acid, and C ₁₈ hydrogenated fatty acid derived from dimerized tung oil. Dimer acid, dimer acid accounts for 70-80% of the total mass of hydrogenated aliphatic dimer acid;

The aminating agent is at least one of hydroxylamine sulfate, hexamethylenediamine, decylamine, and diethylhydroxylamine; the thickening processing aid is maleic rosin, rosin glyceride, hydrogenated rosin glyceride, At least one of pentaerythritol rosin ester, hydrogenated pentaerythritol rosin ester, and acrylic acid modified rosin

[Claim 2] A method for preparing a re-heat-processable thermoplastic starch according to claim 1, wherein the specific steps are as follows:

(1) 80-85 parts by weight of starch and 2-3 parts by weight of the aminating agent are refined by a grinder or a micromachine to a powder particle size of 5 μm to obtain an aminated starch;

(2) adding the aminated starch obtained in the step (1) and 10-15 parts by weight of the hydrogenated aliphatic dimer acid to the high-speed mixer, the temperature of the high-speed mixer is raised to 100-120 ° C, and the stirring speed is controlled at 200-300 rpm. Adding glacial acetic acid while stirring, pre-condensing in a high-speed mixer for 30_4 5min, the amount of glacial acetic acid added is controlled to 2-3% of the mass of the hydrogenated aliphatic dimer acid;

(3) adding the pre-polycondensate obtained in the step (2) to the double-stage twin-screw reaction extruder, The first-stage screw reactor temperature is 80-120 ° C, and the crystal of the aminated starch is relaxed to form an amorphous gel powder by the mixing of the screw edge and the barrel, and is polycondensed with the hydrogenated aliphatic dimer acid; 5-0. The devolatilizer is set to 0. 05-0. The devolatilizer is set to 0. 05-0. 08 MPa, a thermoplastic starch which can be repeatedly heat-processed by continuous polycondensation, devolatilization, and extrusion dicing.

[Claim 3] The method for preparing a re-heat-processable thermoplastic starch according to claim 2, wherein: the step (3) of the double-stage twin-screw reaction extruder comprises a first-order reactor and The second-order reactor, the first-order and second-order reactors are closely linked, and only one feed port and one discharge port are provided, wherein the first-order reactor is an anisotropic twin-screw reaction extruder, and the counter-rotating meshing screw elements enable Crystallization of aminated starch forms amorphous gel powder, polycondensation with hydrogenated aliphatic dimer acid; second-order reactor is a co-rotating twin-screw reaction extruder, co-rotating threaded elements make aminated starch and hydrogenated aliphatic The dimer acid is continuously deep-condensed, and the generated moisture and gas are eliminated in time by the two-stage vacuum devolatilizer, thereby achieving continuous polycondensation, devolatilization, and extrusion dicing.