CN114426760A - Hydrolysis-resistant polyester-based composite material and preparation method thereof - Google Patents
Hydrolysis-resistant polyester-based composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114426760A CN114426760A CN202011178971.7A CN202011178971A CN114426760A CN 114426760 A CN114426760 A CN 114426760A CN 202011178971 A CN202011178971 A CN 202011178971A CN 114426760 A CN114426760 A CN 114426760A
- Authority
- CN
- China
- Prior art keywords
- polyester
- based composite
- hydrolysis
- agent
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 229920000728 polyester Polymers 0.000 title claims abstract description 70
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 60
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- XLDBGFGREOMWSL-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediimine Chemical group 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 claims abstract description 19
- 229920001225 polyester resin Polymers 0.000 claims abstract description 17
- 239000004645 polyester resin Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 30
- -1 polybutylene terephthalate Polymers 0.000 claims description 25
- 229920002313 fluoropolymer Polymers 0.000 claims description 15
- 239000004811 fluoropolymer Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 5
- 230000000655 anti-hydrolysis Effects 0.000 claims description 5
- 239000012745 toughening agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920001780 ECTFE Polymers 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- CHJAYYWUZLWNSQ-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;ethene Chemical group C=C.FC(F)=C(F)Cl CHJAYYWUZLWNSQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000012763 reinforcing filler Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003112 inhibitor Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000032683 aging Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a hydrolysis-resistant polyester-based composite material and a preparation method thereof, and the polyester-based composite material comprises the following components in percentage by weight: 30-70 wt% of polyester resin, 1-10 wt% of hydrolysis resistant agent, 1-10 wt% of fluorine-containing polymer and 0-40 wt% of glass fiber, wherein the hydrolysis resistant agent is bis (2, 6-diisopropylphenyl) carbodiimide and/or epoxy resin. The polyester-based composite material has high hydrolysis resistance and efficiency.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a hydrolysis-resistant polyester-based composite material and a preparation method thereof.
Background
Polybutylene terephthalate (PBT) is one of five common engineering plastics. PBT has excellent heat resistance, chemical resistance, weather resistance, and electrical characteristics. In recent years, the demand for PBT has increased rapidly, particularly in the fields of electronics and automotive industry.
However, because of containing ester bonds in PBT molecules, ester bond fracture easily occurs in a damp-heat environment, hydrolysis reaction occurs, molecular chains of the PBT are fractured through hydrolysis, the molecular weight is reduced, and the mechanical and other properties of the material are rapidly and seriously deteriorated, which seriously limits the application of the PBT. Therefore, it is very important to develop a PBT composite material with high hydrolysis resistance.
Chinese patent CN1938361A discloses that a PBT resin having excellent color tone, hydrolysis resistance, transparency, and molding stability is obtained by using a titanium compound and a metal compound of group 2A of the periodic table as catalysts and adjusting the content and blending ratio thereof. The patent takes the improvement of resin as a basis from the polymerization angle, reduces the content of terminal carboxyl, has requirements on both synthesis process and equipment investment, and has limited improvement on hydrolysis resistance.
Chinese patent CN103525031A discloses a glass fiber reinforced flame-retardant hydrolysis-resistant PBT material and a preparation method thereof, wherein a chain extender (acrylate multipolymer LP2500) is added to reduce the content of terminal carboxyl groups and improve the hydrolysis resistance. However, the PBT material obtained in the patent has low hydrolysis resistance, and the chain extender has strong tackifying effect, which affects material fluidity and increases processing difficulty.
Chinese patent CN102585454A discloses an hydrolysis-resistant continuous fiber reinforced polybutylene terephthalate material, wherein an epoxy compound is used as a cross-linking agent, and polycarbodiimide is used as an hydrolysis-resistant agent. The polycarbodiimide is a common hydrolysis resistant agent, is expensive, and has a common hydrolysis resistant effect if the addition amount is small, and easily generates carbide to influence processing and forming if the addition amount is large.
Chinese patent CN104119648A discloses a hydrolysis-resistant and low-shrinkage glass fiber reinforced flame-retardant PBT and a preparation method thereof, a brominated epoxy flame retardant is added, the epoxy group of the brominated epoxy flame retardant is used for inhibiting the hydrolysis of the PBT, and a flaky mineral filler is added as a shielding agent to isolate the permeation of water vapor. However, the mineral filler cannot isolate moisture and has a great influence on the material performance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a hydrolysis-resistant polyester-based composite material and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
In one aspect, the present invention provides a polyester-based composite material resistant to hydrolysis, wherein the polyester-based composite material comprises, by weight of the polyester-based composite material: 30-70 wt% of polyester resin, 1-10 wt% of hydrolysis resistant agent, 1-10 wt% of fluorine-containing polymer and 0-40 wt% of glass fiber, wherein the hydrolysis resistant agent is bis (2, 6-diisopropylphenyl) carbodiimide and/or epoxy resin.
Hydrolysis of polyester materials such as PBT starts from wetting of moist hot water vapor on the materials, after the moisture is immersed into the materials from the surfaces, water molecules attack ester bonds in polyester molecular chain segments, the ester bonds are broken, and hydrolysis occurs. Under the acidic condition, the hydrolysis is accelerated, and the terminal carboxyl group accelerates the hydrolysis reaction. The inventor of the present application finds that by introducing specific amounts of hydrolysis resistance agent and fluoropolymer into a polyester-based composite material such as PBT, the hydrolysis resistance and efficiency of the polyester-based composite material are significantly improved, and the application of the polyester-based composite material such as PBT in a high temperature and high humidity environment is greatly expanded. Without wishing to be bound by theory, it is believed that in the polyester-based composite material of the present invention, the fluoropolymer has low surface free energy and strong hydrophobicity, and can effectively reduce the surface polarity of the polyester-based composite material, reduce the water contact angle, and form a layer of "hydrophobic film" on the surface of the polyester-based composite material, so that water molecules are not easily attached to the surface of the material, and thus are not easily immersed into the interior of the polyester-based composite material, and moisture in the polyester-based composite material is controlled at an extremely low level, thereby preventing hydrolysis reaction at high temperature. Meanwhile, the hydrolysis resistant agent can capture moisture (water molecules) immersed in the polyester-based composite material, consume carboxyl generated by hydrolysis, and reconnect molecular chain segments, so that the hydrolysis resistance of the polyester-based composite material is improved.
According to the polyester-based composite material provided by the invention, the polyester resin is one or more selected from polybutylene terephthalate (PBT), polyethylene terephthalate, 1, 4-cyclohexanedimethanol ester and polybutylene terephthalate-isophthalate.
In some preferred embodiments, the polyester resin is polybutylene terephthalate. In the present invention, the viscosity of polybutylene terephthalate suitable for the polyester-based composite material of the present invention is 0.72 to 1.30dl/g, preferably 0.85 to 1.0 dl/g. Polybutylene terephthalate is commercially available, for example, from the blue star company under the trade name PBT 1084.
In some preferred embodiments, the polybutylene terephthalate content of the polyester-based composite material may be 30 to 70% by weight, preferably 50 to 70% by weight, and more preferably 60 to 70% by weight.
According to the polyester-based composite material provided by the invention, the hydrolysis resisting agent can be one or both of bis (2, 6-diisopropylphenyl) carbodiimide and epoxy resin, the bis (2, 6-diisopropylphenyl) carbodiimide can capture water and acid generated in the hydrolysis process, and the epoxy resin can react with the terminal carboxyl group to reconnect the polyester chain segments. Preferably, the anti-hydrolysis agent is a mixture of bis (2, 6-diisopropylphenyl) carbodiimide and epoxy resin, and the bis (2, 6-diisopropylphenyl) carbodiimide and the epoxy resin can be compounded to timely and effectively prevent the material from being hydrolyzed.
Examples of epoxy resins suitable for use in the present invention include, but are not limited to, bisphenol a type epoxy resins, such as epoxy resin 0194 available from the blue star company.
According to the polyester-based composite material provided by the invention, the content of the hydrolysis resistant agent in the polyester-based composite material can be 1-10 wt%, and preferably 1-5 wt%. In some embodiments, the hydrolysis resistant agent is a mixture of bis (2, 6-diisopropylphenyl) carbodiimide and an epoxy resin, and the polyester-based composite includes 1 to 3 weight percent bis (2, 6-diisopropylphenyl) carbodiimide and 0.5 to 3 weight percent epoxy resin, and in some embodiments, 1 to 2 weight percent bis (2, 6-diisopropylphenyl) carbodiimide and 0.5 to 1.5 weight percent epoxy resin, with the total content of bis (2, 6-diisopropylphenyl) carbodiimide and epoxy resin being 2.5 to 3.5 weight percent.
According to the polyester-based composite material provided by the invention, the fluorine-containing polymer is one or more selected from Polytetrafluoroethylene (PTFE), Fluorinated Ethylene Propylene (FEP) and ethylene chlorotrifluoroethylene copolymer (ECTFE).
The polyester-based composite material provided by the invention can contain 1-10 wt%, preferably 1-5 wt% of the fluorine-containing polymer.
According to the polyester-based composite material provided by the invention, the fluorine-containing polymer is micropowder with the average particle size of 0.5-15 mu m. It is considered that the use of the fine powder having such a particle size range is advantageous for the sufficient dispersion of the fluorine-containing polymer, and the modulus and strength of the polyester-based composite material can be significantly improved by the combined action with the polyester material. In some preferred embodiments, the fluoropolymer is a polytetrafluoroethylene micropowder having an average particle size of 0.5 to 15 μm.
In the present invention, polytetrafluoroethylene micropowder is commercially available, for example, from 3M under the trade name TF 9205.
According to the polyester-based composite material provided by the invention, the reinforcement can be carried out by adopting glass fibers, and the content of the glass fibers can be 0-40 wt%, and is preferably 10-30 wt%.
Examples of glass fibers suitable for use in the present invention include, but are not limited to, alkali-free glass fibers. The diameter of the alkali-free glass fiber may be 10 to 15 μm. Alkali-free glass fibers are commercially available, for example, as long alkali-free glass fibers having a diameter of 13.5 μm from Taishan glass fibers company under the trade designation EDR 200-13.5-T635C.
According to the polyester-based composite material provided by the invention, an auxiliary agent can be used in the polyester-based composite material, and the amount of the auxiliary agent can be 1-10 wt%, and preferably 1-5 wt%.
Suitable auxiliaries for use in the present invention may be antioxidants, heat stabilizers, ultraviolet light stabilizers, colorants including dyes and pigments, mold release agents, lubricants, plasticizers, dispersing aids, reinforcing fillers, flow modifiers, flame retardants, or combinations thereof. In the present invention, any specific auxiliary known in the art may be used. In some embodiments, the polyester-based composite includes 2 to 4 weight percent toughener and 0.1 to 1 weight percent antioxidant.
Tougheners suitable for use in the present invention are commercially available, for example, from DuPont under the trade name DuPont
Toughener of PTW.
In the present invention, the antioxidants may be used alone or in combination. For example, antioxidant 1010 from BASF and antioxidant 627 from Aujeldahl may be used.
As a specific embodiment of the present invention, the polyester-based composite material comprises, based on the weight of the polyester-based composite material: 61.6 wt.% PBT resin, 2 wt.% bis (2, 6-diisopropylphenyl) carbodiimide, 0.5 wt.% epoxy resin, 3 wt.% polytetrafluoroethylene, 30 wt.% glass fiber, 2.5 wt.% toughening agent and 0.4 wt.% antioxidant.
On the other hand, the invention also provides a preparation method of the hydrolysis-resistant polyester-based composite material, wherein the preparation method further comprises the following steps:
(1) mixing polyester resin, an anti-hydrolysis agent, a fluorine-containing polymer and an optional auxiliary agent to obtain a mixed material;
(2) and (2) adding the mixed material obtained in the step (1) into an extruder, adding glass fiber, and performing melt extrusion, bracing, cooling and granulation to obtain the hydrolysis-resistant polyester-based composite material.
The preparation method provided by the invention further comprises the following steps:
(3) these raw materials are dried at a temperature of 80-120 c, for example, for 2-4 hours, to control the moisture < 0.05%, before mixing the polyester resin, hydrolysis resistance agent, fluoropolymer and optionally auxiliaries.
According to the preparation method provided by the invention, in the step (1), the polyester resin, the anti-hydrolysis agent, the fluorine-containing polymer and the auxiliary are mixed by a method comprising the following steps:
(101) premixing polyester resin and fluorine-containing polymer in a high-speed mixer to obtain a premixed material;
(102) adding the hydrolysis resistant agent and the auxiliary agent into the pre-mixed material and continuously mixing to obtain a mixed material.
In the present invention, the fluoropolymer having high hydrophobicity is first mixed with the polyester resin, which is advantageous in that the fluoropolymer is sufficiently and uniformly dispersed in the polyester resin (polyester-based composite material).
According to the preparation method provided by the invention, the extruder in the step (2) is a double-screw extruder. In the invention, the double-screw extruder is adopted, which is beneficial to ensuring that the prepared composite material has good material performance.
In some embodiments, the length to diameter ratio of the extruder in step (2) is from 32 to 48:1, the melt extrusion temperature is from 200 to 270 ℃, the vacuum is > 0.05MPa, and the screw speed of the extruder is from 180 to 600 rpm.
The invention has the following advantages:
(1) the polyester-based composite material of the invention introduces the hydrolysis resistant agent and the fluorine-containing polymer, remarkably improves the hydrolysis resistance and efficiency of the polyester-based composite material, and greatly expands the application of the polyester-based composite material such as PBT in high-temperature and high-humidity environment.
(2) Compared with the existing PBT composite material, the polyester-based composite material disclosed by the invention has the advantages that the hydrolysis resistance of the composite material is comprehensively improved from the aspects of water resistance, water resistance and water absorption, the polyester-based composite material is a high-hydrolysis-resistance polyester-based composite material, and the application of the polyester-based composite material such as PBT in a high-temperature high-humidity environment is greatly expanded.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Examples 1 to 8
1. And (5) drying the raw materials.
Respectively drying the PBT resin, the anti-hydrolysis agent, the fluorine-containing polymer and the auxiliary agent at 80 ℃ for 4 hours in vacuum so that the moisture of each raw material is less than 0.05 percent.
2. And (4) preparing a mixed material.
2.1 PolyPBT resin and fluoropolymer are premixed in a high-speed mixer to obtain a premixed material.
2.2 adding the hydrolysis-resistant agent and the auxiliary agent into the pre-mixed material and continuously mixing to obtain a mixed material.
3. And (4) extruding and granulating.
Adding the mixed material into a double-screw extruder with the length-diameter ratio of 40:1, adding glass fiber, and performing melt extrusion, bracing, cooling and granulation to obtain the PBT composite material, wherein the melt extrusion temperature is 235 ℃, the vacuum degree is 0.08MPa, and the screw rotating speed of the extruder is 320 rpm.
The starting materials used in examples 1 to 8 are shown in Table 1.
Comparative examples 1 to 3
PBT composites were prepared in substantially the same manner as in examples 1-8, using the starting materials shown in Table 1.
Performance testing
The composite particles obtained in examples 1 to 8 and comparative examples 1 to 3 were dried and then molded into standard sample bars by an injection molding machine to carry out the test. The test method used was as follows: testing tensile strength according to ASTM D638; notched bar impact strength was measured according to ASTM D256.
Hydrolysis resistance and aging test: and (3) placing the stretched and notched impact sample strip into a constant temperature and humidity box, aging for 1000 hours at the temperature of 85 ℃ and the humidity of 85%, then taking out the sample strip, standing for 24 hours at normal temperature, and then performing stretching and impact tests according to the standard. The test results are shown in table 1.
Table 1: formulations and Properties of the composites of examples 1-8 and comparative examples 1-3
Note: (1) data after 1000 hours of damp heat aging, aging was carried out at 85 ℃ and 85% humidity.
As is clear from comparison in Table 1, in comparative examples 1 to 3 in which the fluoropolymer, the epoxy resin and the bis (2, 6-diisopropylphenyl) carbodiimide were not added at the same time, the retention rates of the tensile strength by wet heat aging were 77.3%, 86.5% and 80.6%, respectively, and the retention rates of the notched impact strength were 59.2%, 72.6% and 62.8%, respectively. In contrast, the tensile and notched impact strength retention rates for the PBT composites of examples 1-8 after humid heat aging were both greater than 85%, and the PBT composites had significantly improved hydrolytic resistance and efficiency.
Further, as can be seen from examples 1 to 4 and comparative example 2, the moisture-heat aging retention of tensile strength and notched impact strength of the PBT composite material is relatively low due to the too small amount of the fluoropolymer, which may be attributed to: the amount of the fluorine-containing polymer is not enough to form a uniform 'hydrophobic film' on the surface of the PBT composite material, and the moist and hot water vapor breaks the protection of the first layer and permeates into the material to influence the hydrolysis resistance effect. However, the use of higher amounts of fluoropolymer leads to an overall decrease in the mechanical properties of the PBT composite.
As can be seen from examples 3 and 5 to 6, when the amount of bis (2, 6-diisopropylphenyl) carbodiimide used was increased from 1% by weight to 3% by weight, the retention rate of wet heat aging of tensile strength and notched impact strength of the PET composite material was increased and then decreased.
In addition, the embodiment 5 provides the best hydrolysis resistance, the initial tensile strength and the notch impact strength are high, the performance retention rate after aging is optimal, the hydrolysis resistance of the PBT composite material is obviously improved, and the application of the PBT material in a high-temperature high-humidity environment is successfully expanded.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A hydrolysis resistant polyester-based composite, wherein the polyester-based composite comprises, by weight of the polyester-based composite: 30-70 wt% of polyester resin, 1-10 wt% of hydrolysis resistant agent, 1-10 wt% of fluorine-containing polymer and 0-40 wt% of glass fiber, wherein the hydrolysis resistant agent is bis (2, 6-diisopropylphenyl) carbodiimide and/or epoxy resin.
2. The polyester-based composite according to claim 1, wherein the polyester resin is one or more selected from the group consisting of polybutylene terephthalate (PBT), polyethylene terephthalate, 1, 4-cyclohexanedimethanol ester, polybutylene terephthalate-isophthalate;
preferably, the polyester resin is polybutylene terephthalate;
more preferably, the viscosity of the polybutylene terephthalate is 0.72-1.30 dl/g, and preferably 0.85-1.0 dl/g;
more preferably, the polybutylene terephthalate is present in an amount of 50 to 70 wt.%, preferably 60 to 70 wt.%.
3. The polyester-based composite according to claim 1 or 2, wherein the content of the hydrolysis inhibitor in the polyester-based composite is 1 to 5% by weight.
4. The polyester-based composite according to any one of claims 1 to 3, wherein the hydrolysis resistance agent is a mixture of bis (2, 6-diisopropylphenyl) carbodiimide and an epoxy resin;
preferably, the polyester-based composite comprises 1 to 3 weight percent bis (2, 6-diisopropylphenyl) carbodiimide and 0.5 to 3 weight percent epoxy resin;
more preferably, the polyester-based composite comprises 1 to 2 weight percent bis (2, 6-diisopropylphenyl) carbodiimide and 0.5 to 1.5 weight percent epoxy resin, the total content of bis (2, 6-diisopropylphenyl) carbodiimide and epoxy resin being 2.5 to 3.5 weight percent;
preferably, the epoxy resin is a bisphenol a type epoxy resin.
5. The polyester-based composite according to any one of claims 1 to 4, wherein the fluoropolymer is one or more selected from polytetrafluoroethylene, polyperfluoroethylpropylene, and ethylene chlorotrifluoroethylene copolymer;
preferably, the fluoropolymer is present in an amount of 1 to 5 wt%;
preferably, the fluoropolymer is a fine powder having an average particle diameter of 0.5 to 15 μm.
6. The polyester-based composite according to any one of claims 1 to 5, wherein the content of the glass fiber is 10-30 wt%;
preferably, the glass fibers are alkali-free glass fibers;
more preferably, the alkali-free glass fibers have a diameter of 10 to 15 μm.
7. The polyester-based composite according to any one of claims 1 to 6, wherein the polyester-based composite comprises 1-10 wt. -%, preferably 1-5 wt. -% of auxiliaries;
preferably, the auxiliary agent is an antioxidant, a heat stabilizer, an ultraviolet light stabilizer, a colorant, a mold release agent, a lubricant, a plasticizer, a dispersion auxiliary agent, a reinforcing filler, a flow modifier, a flame retardant, or a combination thereof;
preferably, the polyester-based composite material comprises 2 to 4 weight percent of toughening agent and 0.1 to 1 weight percent of antioxidant.
8. The polyester-based composite according to any one of claims 1 to 7, wherein the polyester-based composite comprises, based on the weight of the polyester-based composite: 61.6 wt.% PBT resin, 2 wt.% bis (2, 6-diisopropylphenyl) carbodiimide, 0.5 wt.% epoxy resin, 3 wt.% polytetrafluoroethylene, 30 wt.% glass fiber, 2.5 wt.% toughening agent and 0.4 wt.% antioxidant.
9. The method for preparing the polyester-based composite material according to any one of claims 1 to 8, wherein the method further comprises the steps of:
(1) mixing polyester resin, an anti-hydrolysis agent, a fluorine-containing polymer and an optional auxiliary agent to obtain a mixed material;
(2) and (2) adding the mixed material obtained in the step (1) into an extruder, adding glass fiber, and performing melt extrusion, bracing, cooling and granulation to obtain the hydrolysis-resistant polyester-based composite material.
10. The method of manufacturing of claim 9, wherein the method of manufacturing further comprises the steps of:
(3) drying these raw materials at a temperature of 80-120 ℃ for, for example, 2-4 hours to control the moisture content to < 0.05% before mixing the polyester resin, the hydrolysis resistance agent, the fluoropolymer and optionally the auxiliaries;
preferably, the polyester resin, the hydrolysis resistance agent, the fluoropolymer and the auxiliary are mixed in step (1) by a method comprising the steps of:
(101) premixing polyester resin and fluorine-containing polymer in a high-speed mixer to obtain a premixed material;
(102) adding the hydrolysis resistant agent and the auxiliary agent into the pre-mixed material and continuously mixing to obtain a mixed material;
preferably, the extruder in step (2) is a twin-screw extruder;
more preferably, the length-diameter ratio of the extruder in the step (2) is 32-48:1, the temperature of melt extrusion is 200-270 ℃, the vacuum degree is more than 0.05MPa, and the screw rotating speed of the extruder is 180-600 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011178971.7A CN114426760A (en) | 2020-10-29 | 2020-10-29 | Hydrolysis-resistant polyester-based composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011178971.7A CN114426760A (en) | 2020-10-29 | 2020-10-29 | Hydrolysis-resistant polyester-based composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114426760A true CN114426760A (en) | 2022-05-03 |
Family
ID=81309053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011178971.7A Pending CN114426760A (en) | 2020-10-29 | 2020-10-29 | Hydrolysis-resistant polyester-based composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114426760A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028970A (en) * | 2022-06-09 | 2022-09-09 | 湖北合聚新材料有限公司 | PBT material, preparation method thereof and micro-nano laminated co-extrusion device |
| CN115197550A (en) * | 2022-07-20 | 2022-10-18 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant polyester resin composition and preparation method thereof |
| CN115785627A (en) * | 2022-11-30 | 2023-03-14 | 江苏金发科技新材料有限公司 | Hydrolysis-resistant polyester resin composite material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566865A (en) * | 2015-12-29 | 2016-05-11 | 佛山市顺德区美的洗涤电器制造有限公司 | Wear and hydrolysis resistant PBT material, preparation method thereof, bowl blanket and dish washing machine |
| CN109777051A (en) * | 2018-12-28 | 2019-05-21 | 江苏博云塑业股份有限公司 | A kind of polyester composite of hydrolysis and preparation method thereof |
| CN113667283A (en) * | 2021-07-16 | 2021-11-19 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant reinforced PBT resin and preparation method and application thereof |
| CN115197550A (en) * | 2022-07-20 | 2022-10-18 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant polyester resin composition and preparation method thereof |
-
2020
- 2020-10-29 CN CN202011178971.7A patent/CN114426760A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566865A (en) * | 2015-12-29 | 2016-05-11 | 佛山市顺德区美的洗涤电器制造有限公司 | Wear and hydrolysis resistant PBT material, preparation method thereof, bowl blanket and dish washing machine |
| CN109777051A (en) * | 2018-12-28 | 2019-05-21 | 江苏博云塑业股份有限公司 | A kind of polyester composite of hydrolysis and preparation method thereof |
| CN113667283A (en) * | 2021-07-16 | 2021-11-19 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant reinforced PBT resin and preparation method and application thereof |
| CN115197550A (en) * | 2022-07-20 | 2022-10-18 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant polyester resin composition and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028970A (en) * | 2022-06-09 | 2022-09-09 | 湖北合聚新材料有限公司 | PBT material, preparation method thereof and micro-nano laminated co-extrusion device |
| CN115197550A (en) * | 2022-07-20 | 2022-10-18 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant polyester resin composition and preparation method thereof |
| CN115197550B (en) * | 2022-07-20 | 2024-04-02 | 上海金山锦湖日丽塑料有限公司 | Hydrolysis-resistant polyester resin composition and preparation method thereof |
| CN115785627A (en) * | 2022-11-30 | 2023-03-14 | 江苏金发科技新材料有限公司 | Hydrolysis-resistant polyester resin composite material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114426760A (en) | Hydrolysis-resistant polyester-based composite material and preparation method thereof | |
| CN112266619B (en) | Polycarbonate composition resistant to wet heat aging and preparation method thereof | |
| CN109608833B (en) | High-strength flame-retardant PCT engineering plastic and preparation method thereof | |
| CN109666291A (en) | A kind of low water suction nylon 6 composite material of high rigidity | |
| WO2015064482A1 (en) | Molded article and molding material | |
| CN113652062B (en) | PBT/PC alloy with stable mechanical property, preparation method and product thereof | |
| CN111484719A (en) | High-impact-resistance flame-retardant reinforced polycarbonate composite material and preparation method thereof | |
| CN109897347B (en) | Military electric connector insulator and preparation method thereof | |
| CN110499010A (en) | A kind of glass fiber-reinforced polycarbonate composite material and preparation method and application | |
| CN101165093A (en) | High hydrolysis resistance anti-flaming enhanced polybutylene terephthalate composition and preparation method thereof | |
| CN109749372A (en) | A kind of fire-retardant reinforced PBT composite material and preparation method thereof | |
| CN112194845A (en) | Halogen flame-retardant reinforced polypropylene composite material and preparation method thereof | |
| CN111484722A (en) | High-impact-resistance flame-retardant reinforced PC/ABS alloy material and preparation method thereof | |
| CN110791049A (en) | Flame-retardant reinforced polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN114591567B (en) | Glass fiber reinforced flame-retardant polypropylene composite material and preparation method and application thereof | |
| CN105017764A (en) | Composite material of halogen-free flame-retardant reinforced PA66/recycled PET bottle-grade chips and preparation method thereof | |
| CN110760177B (en) | Conductive polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| Varga et al. | Improving mechanical properties of glass fibre reinforced PBT waste for its recycling as a product of pipe system elements | |
| CN106479035B (en) | Flame-retardant impact-resistant polypropylene composite material and preparation method thereof | |
| CN1824706A (en) | Preparation method of polycarbonate/acrylonitrile butadiene-vinylbenzene resin mixture | |
| CN111057358B (en) | High-heat-resistance impact-resistance polycarbonate composition and preparation method thereof | |
| CN110591267B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ASA material with excellent weather resistance and preparation method thereof | |
| CN112143032B (en) | Modified aluminum hydroxide, flame-retardant polyvinyl chloride material and preparation method thereof | |
| CN113278225A (en) | Nano-silica reinforced PP (polypropylene) material and preparation process thereof | |
| CN110819083B (en) | High-mechanical-property flame-retardant reinforced PET and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |