CN111909459A - Double-effect hydrolysis-resistant master batch and preparation method thereof - Google Patents
Double-effect hydrolysis-resistant master batch and preparation method thereof Download PDFInfo
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- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 66
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 65
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title description 6
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000002667 nucleating agent Substances 0.000 claims abstract description 28
- 230000000655 anti-hydrolysis Effects 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- -1 Polyethylene Polymers 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 239000004626 polylactic acid Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 150000001718 carbodiimides Chemical class 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229920002961 polybutylene succinate Polymers 0.000 claims description 4
- 239000004631 polybutylene succinate Substances 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 229920000704 biodegradable plastic Polymers 0.000 claims description 3
- 229920006351 engineering plastic Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002193 fatty amides Chemical class 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000010452 phosphate Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 6
- 239000004593 Epoxy Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000004513 sizing Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C=NC1=C(C(C)C)C=CC=C1C(C)C XLDBGFGREOMWSL-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
Abstract
The invention discloses a double-effect hydrolysis-resistant master batch which mainly comprises 100 parts of carrier resin, 1-5 parts of nucleating agent and 10-50 parts of hydrolysis-resistant agent. The performance of the hydrolysis-resistant master batch system is improved by comprehensively adopting two physical and chemical modes, the physical mode is increased, namely the crystallinity of the polymer is improved by adding the nucleating agent while the hydrolysis degree is reduced by adding the hydrolysis-resistant agent in a chemical mode, and the increase of the crystallinity is beneficial to reducing an amorphous area, so that the permeation of water molecules is reduced, and the hydrolysis degree is reduced. When the anti-hydrolysis master batch is prepared, the carrier and the auxiliary agent are adhered together by a hot melting method to achieve a state of uniform mixing and no separation, and the anti-hydrolysis master batch is obtained by cooling, sizing, melting, extruding and granulating, so that the mixing uniformity of the carrier and the auxiliary agent can be remarkably improved. When the hydrolysis-resistant master batch is used for producing polylactic resin, the tensile property of the resin is obviously improved.
Description
Technical Field
The invention mainly relates to the technical field of high polymer materials, in particular to a master batch with double effects of promoting crystallization and resisting hydrolysis and a preparation technology thereof.
Background
Polycondensation resins, particularly resins such as polyethylene terephthalate (PET), Polyamide (PA), polylactic acid (PLA), and the like, have excellent physical and mechanical properties and are widely used in various industrial and domestic fields. In the actual processing and using process, the resin inevitably reacts with water molecules under high-temperature and high-humidity environment, so that the resin is degraded, and simultaneously, carboxyl and the like generated by degradation catalyze the further breaking degradation of molecular chains more quickly, and finally, the processing and using performance of products are lost.
At present, the industry adds an anti-hydrolysis agent to solve the common problem, but the direct addition of the anti-hydrolysis agent has various disadvantages. Firstly, the anti-hydrolysis agent is mostly in a powder form, and is difficult to be mixed with resin particles to achieve a uniform degree, so that local concentration is not uniform; secondly, due to the difference of the shape and the specific gravity of the hydrolysis resistant agent powder and the resin particles at the processing feeding end, the blanking speeds of the hydrolysis resistant agent powder and the resin particles are not consistent, and the stability of the processing and using performances cannot be met; thirdly, the use of the powder is easy to cause pollution to the operating environment and inaccurate metering caused by powder adhesion in the processing process; fourthly, the monomeric hydrolysis resistant agent has a low melting point, and is easy to melt and agglomerate due to high environmental temperature in the transportation and feeding processes, thereby causing difficult use and blockage of a feeding port.
Based on the defects, the masterbatching of the hydrolysis-resistant system is the best mode for solving the problems, and has the advantages of uniform mixing, convenient storage and transportation, accurate metering, environmental friendliness and the like. At present, polyester hydrolysis-resistant master batches mainly comprise an hydrolysis-resistant agent and a polyester carrier as main components, and are obtained by melt extrusion, and are described in detail in patents ZL201310703078.5 and ZL 201410372942.2. However, this process still has several drawbacks. Firstly, a carrier is polycondensation resin, and terminal carboxyl groups exposed by a molecular chain are easy to react with an anti-hydrolysis agent, so that the efficiency is reduced in the preparation process of the master batch; secondly, in the storage process of the master batch, the exposed carboxyl end groups of the molecular chain of the polyester carrier react with the hydrolysis-resistant agent or the hydrolysis reaction occurs due to the water absorption characteristic of ester groups in the molecular chain, so that the efficiency of the hydrolysis-resistant agent is reduced; thirdly, the processing temperature of the polyester carrier is generally high, and the monomer type carbodiimide hydrolysis-resistant agent is extremely easy to decompose at the temperature, so that harmful gas is generated to pollute the environment; fourthly, the hydrolysis problem of the polyester is solved only by a chemical mode, no physical mode is involved, and the solution is not comprehensive; fifth, the prior art is completed by simply mixing the carrier and the auxiliary agent and then adding the mixture into an extruder for granulation, and the problem of uneven simple mixing of the auxiliary agent powder and the granular carrier caused by the shape and the specific gravity difference is not solved.
Disclosure of Invention
In order to solve one or more of the problems, the invention discloses a double-effect hydrolysis-resistant master batch which mainly comprises 100 parts of carrier resin, 1-5 parts of nucleating agent and 10-50 parts of hydrolysis-resistant agent.
Wherein the carrier resin is a granular or powdery thermoplastic resin, and comprises one or a mixture of polyolefin, engineering plastics and bio-based and biodegradable plastics. Polyolefins including Polyethylene (PE), polypropylene (PP), long carbon paraffin waxes, fatty amide resins; the engineering plastics comprise Polyamide (PA) and polyethylene terephthalate (PET) resin; the bio-based and biodegradable plastics include polylactic acid (PLA), polybutylene terephthalate-adipate (PBAT), polypropylene carbonate (PPC), and polybutylene succinate (PBS) resin. The polypropylene resin is inert resin, does not contain exposed carboxyl end groups, and cannot react with an anti-hydrolysis agent in the preparation process of the master batch, so that the degradation of the anti-hydrolysis performance of the master batch is avoided, and therefore, the non-polar Powdery Polypropylene (PP) is preferably selected as the carrier resin.
The nucleating agent is one or a mixture of more of inorganic powder nucleating agents, organic compounds nucleating agents and high polymer material nucleating agents. The inorganic powder includes spherical or fibrous filler such as calcium carbonate, pulvis Talci, mica, montmorillonite, barium sulfate, and glass fiber. The organic compound nucleating agent comprises high-melting-point organic salt nucleating agents such as substituted benzoate, phosphate and aryl phosphonate which are suitable for polycondensation resin. The high molecular material nucleating agent comprises high melting point or high molecular weight thermoplastic resin. Aryl phosphonate nucleating agents are preferred in the present invention.
The anti-hydrolysis agent is one or more of compounds containing carbodiimide, isocyanate, epoxy group, anhydride group and the like or polymer. Wherein the carbodiimide comprises one or more of monomeric carbodiimide, bis-carbodiimide or polymeric carbodiimide, and the invention preferably selects monomeric carbodiimide 2,2', 6,6' -tetraisopropyldiphenylcarbodiimide.
The invention also provides a preparation method of the double-effect hydrolysis-resistant master batch, which comprises the following steps:
(1) heating the carrier resin in a dryer, heating to a temperature higher than the melting point of the hydrolysis-resistant agent by more than 10-30 ℃, and keeping for 1-2 hours;
(2) adding the hot carrier resin, the anti-hydrolysis agent and the nucleating agent into a high-speed mixer, quickly and uniformly stirring, controlling the rotating speed from low to high at (400-;
(3) and (3) adopting a double-screw extruder, and performing melt extrusion and granulation on the shaped material under the conditions that the temperature ranges from 180 ℃ to 230 ℃ and the screw rotating speed is from 300 to 600rpm to obtain the double-effect hydrolysis-resistant master batch.
Particularly, the invention also relates to application of the double-effect hydrolysis-resistant master batch in hydrolysis-resistant polylactic resin, wherein the hydrolysis-resistant master batch is added into the polylactic resin according to the content of 2%, extrusion granulation is carried out to obtain the hydrolysis-resistant polylactic resin, a hydrolysis resistance test is carried out in a constant-temperature water bath tank at the temperature of 50 ℃, and the tensile strength degradation of the polylactic resin is lower than 5% after 20 days.
The invention comprehensively adopts two physical and chemical modes to improve the performance of a hydrolysis-resistant master batch system, on one hand, the crystallization degree of the polymer is improved by adding the nucleating agent in the physical mode, and the increase of the crystallization degree is beneficial to reducing an amorphous area, therebyThe penetration of water molecules is reduced, and the hydrolysis degree is reduced; the other partyNoodleThe hydrolysis resistant agent is added in a chemical mode, so that the crystallinity is improved, and the hydrolysis resistant performance is achieved. When the hydrolysis-resistant master batch is prepared, the carrier and the auxiliary agent are adhered together by a hot melting method to achieve a state of uniform mixing and no separation, and the hydrolysis-resistant master batch is obtained by cooling and sizing and then by a melt extrusion granulation method, so that the mixing uniformity of the carrier and the auxiliary agent is remarkably improved. When the hydrolysis-resistant master batch is used for producing polylactic resin, the tensile property of the resin is obviously improved.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which will assist those skilled in the art to further understand the present invention, but which are only preferred embodiments of the present invention and do not limit the present invention in any way. Therefore, all equivalent changes made according to the characteristics and principles of the invention described in the claims of the present application are included in the scope of the present application.
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention better and clearly understood, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples 1 to 5
The polypropylene powder is used as carrier resin, aryl phosphonate nucleating agent (the nucleating agent sold by Shanxi province chemical research institute (Co., Ltd.) with the brand number of TMC-200) and monomer type carbodiimide 2,2', 6,6' -tetraisopropyl diphenyl carbodiimide hydrolysis-resistant agent (the hydrolysis-resistant agent sold by the Shanxi province chemical research institute (Co., Ltd.) with the brand number of BIO-SW 100) are selected. Maintaining polypropylene powder (T30S) in a dryer at 70 ℃ for 1 hour, then adding the polypropylene powder and a nucleating agent and an anti-hydrolysis agent into a high-speed mixer according to the proportion of 100:1:10, 100:2:20, 100:3:30, 100:4:40 and 100:5:50 respectively, stirring for 2 minutes, cooling and discharging, then adding into a double-screw extruder, and extruding at 200 ℃ and 400rpm to obtain the anti-hydrolysis master batch.
The hydrolysis resistant master batch in the examples 1 to 5 is added into polylactic acid with the content of 2 percent, extruded and granulated at the temperature of 230 ℃ and 180 ℃ to obtain the hydrolysis resistant polylactic resin, and then sample bars are prepared for hydrolysis resistant tests.
Example 6 is a polylactic acid resin without adding a hydrolysis resistant master batch for comparative experiments.
The hydrolysis resistance test is carried out at the temperature of 50 ℃ in a constant-temperature water bath for 20 days, and the tensile strength is tested after the aging test is finished. The specific test results are shown in table 1.
TABLE 1 polylactic acid sample strip aging test
As can be seen from the reduction in the amplitude in table 1, the polylactic acid resin without the hydrolysis resistant master batch in example 6 has 100% of tensile strength reduction after 20 days of aging test, and is completely lost. In examples 1 to 5, the polylactic acid resin added with the hydrolysis-resistant master batch prepared by the method of the present invention has a significant hydrolysis-resistant effect, and the tensile strength degradation is less than 5%, and almost no loss occurs.
Claims (9)
1. The double-effect hydrolysis-resistant master batch is characterized by comprising the following components in parts by weight:
100 parts of carrier resin
1-5 parts of nucleating agent
10-50 parts of an anti-hydrolysis agent.
2. The dual effect hydrolysis resistant masterbatch of claim 1 wherein the carrier resin is a thermoplastic resin in the form of pellets or powder, and is a polyolefin such as Polyethylene (PE), polypropylene (PP), long carbon paraffin wax, fatty amide resin; engineering plastics such as Polyamide (PA), polyethylene terephthalate (PET) resin; a mixture of bio-based and biodegradable plastics such as one or more of polylactic acid (PLA), polybutylene terephthalate-adipate (PBAT), polypropylene carbonate (PPC), polybutylene succinate (PBS) resins.
3. The dual effect hydrolysis resistant masterbatch of claim 2 wherein said carrier resin is preferably a non-polar Powdered Polypropylene (PP) resin.
4. The double-effect hydrolysis-resistant master batch as claimed in claim 1, wherein the nucleating agent is one or more of inorganic powder nucleating agents, organic compound nucleating agents and high molecular material nucleating agents: wherein the inorganic powder nucleating agent is a spherical or fibrous filling material and is one or more of calcium carbonate, talcum powder, mica, montmorillonite, barium sulfate and glass fiber; the organic compound nucleating agent is high-melting-point organic salt nucleating agent suitable for polycondensation resin, and comprises one or more of substituted benzoate, phosphate and aryl phosphonate; the high molecular material nucleating agent is high-melting point or high molecular thermoplastic resin.
5. The dual effect hydrolysis resistant masterbatch of claim 4 wherein said nucleating agent is preferably an aryl phosphonate type nucleating agent.
6. The dual effect hydrolysis resistant masterbatch of claim 1 wherein the hydrolysis resistant agent is one or more mixtures of compounds or polymers containing carbodiimide, isocyanate, epoxy, anhydride groups, wherein the hydrolysis resistant agent is preferably one or more mixtures of monomeric, bis-or polymeric carbodiimide.
7. The double effect hydrolysis resistant masterbatch according to claim 7, wherein said hydrolysis resistant agent is preferably monomeric carbodiimide 2,2'6,6' -tetraisopropyl diphenyl carbodiimide.
8. A method of making a dual effect hydrolysis resistant masterbatch as claimed in any one of claims 1 to 7 comprising the steps of:
(1) heating the carrier resin in a dryer, heating to a temperature higher than the melting point of the hydrolysis-resistant agent by more than 10-30 ℃, and keeping for 1-2 hours;
(2) adding the hot carrier resin, the anti-hydrolysis agent and the nucleating agent into a high-speed mixer, quickly and uniformly stirring, controlling the rotation speed from low to high at (400-;
(3) and (3) adopting a double-screw extruder, and performing melt extrusion and granulation on the shaped material under the conditions that the temperature ranges from 180 ℃ to 230 ℃ and the screw rotating speed is from 300 to 600rpm to obtain the double-effect hydrolysis-resistant master batch.
9. The use of a dual effect hydrolysis resistant masterbatch in a hydrolysis resistant polylactic acid resin according to any one of claims 1-7, wherein the hydrolysis resistant masterbatch is added to the polylactic acid resin at a content of 2%, extrusion granulation is performed to obtain the hydrolysis resistant polylactic acid resin, and then a hydrolysis resistance test is performed in a constant temperature water bath at 50 ℃, and after 20 days, the tensile strength of the polylactic acid resin is reduced by less than 5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113831712A (en) * | 2021-10-25 | 2021-12-24 | 海信容声(广东)冰箱有限公司 | Hydrolysis-resistant polylactic acid material and preparation method and application thereof |
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| CN106589861A (en) * | 2015-10-16 | 2017-04-26 | 汉达精密电子(昆山)有限公司 | Biodegradable resin material and product thereof |
| CN107674392A (en) * | 2017-09-22 | 2018-02-09 | 浙江闪铸三维科技有限公司 | A kind of plasticizing polylactic acid 3D printing material and preparation method thereof |
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- 2020-09-04 CN CN202010920665.XA patent/CN111909459A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589861A (en) * | 2015-10-16 | 2017-04-26 | 汉达精密电子(昆山)有限公司 | Biodegradable resin material and product thereof |
| CN107674392A (en) * | 2017-09-22 | 2018-02-09 | 浙江闪铸三维科技有限公司 | A kind of plasticizing polylactic acid 3D printing material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 耿孝正: "《双螺杆挤出机及其应用》", 31 January 2003, 中国轻工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113831712A (en) * | 2021-10-25 | 2021-12-24 | 海信容声(广东)冰箱有限公司 | Hydrolysis-resistant polylactic acid material and preparation method and application thereof |
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