CN116396591B - Preparation method of reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof and product thereof - Google Patents
Preparation method of reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof and product thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002667 nucleating agent Substances 0.000 claims abstract description 60
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 47
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 39
- 239000003365 glass fiber Substances 0.000 claims abstract description 37
- 238000001125 extrusion Methods 0.000 claims abstract description 23
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000010899 nucleation Methods 0.000 claims abstract description 14
- 230000006911 nucleation Effects 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 6
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 81
- 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 26
- 239000001993 wax Substances 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920003182 Surlyn® Polymers 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 2-dodecanoyloxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCC ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012170 montan wax Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 229920006228 ethylene acrylate copolymer Polymers 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 68
- 239000002994 raw material Substances 0.000 description 16
- 239000000314 lubricant Substances 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 13
- 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 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
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- 238000007599 discharging Methods 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 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 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000467686 Eschscholzia lobbii Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- 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
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof and a product thereof. Comprises the following components in parts by weight: 100 parts of PET resin, 45-65 parts of glass fiber, 10-25 parts of filling powder, 0.6-2 parts of self-made nucleating agent, 2-4 parts of nucleating accelerator, 1.8 parts of organic wax, 0.8 part of primary antioxidant, 0.4 part of auxiliary antioxidant and 3.8 parts of toughening agent. The resin, the nucleating agent, the nucleation accelerator, the organic wax and the antioxidant are uniformly mixed and fed through a main feed opening, powder is filled, glass fiber is fed from two sides, and after double-screw extrusion granulation, the reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof can be prepared, and the CLTE in the vertical flow direction is smaller than 6 multiplied by 10 ‑5K‑1, and the anisotropy thereof is small, so that the requirement of kitchen electrical products on small size change of products in the alternating use process of cold and heat is completely met.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of a reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof and a product thereof.
Background
PET (polyethylene terephthalate) chips are amorphous materials, mainly for fibers, and in small amounts for films and engineering plastics.
Due to the rigidity of the molecular chain structure of PET, the crystallization speed of PET is slow, the crystallization temperature is high, and the crystallinity is low. By adding the nucleating agent and the nucleating accelerator, the crystallization speed is improved, the crystallinity is improved, and meanwhile, by adding the glass fiber and the mineral filler, engineering application can be realized, and the glass fiber composite material is applied to the electronic appliance and automobile industries and is used for various coil frameworks, transformers, kitchen appliances, automobile rearview mirrors, automobile wipers and the like. However, if the nucleating agent, the nucleating accelerator and the reinforcing agent are unreasonably selected, or the material nucleating efficiency is insufficient, the injection molding processing is mold sticking, the injection molding efficiency is low, the temperature resistance can not meet the application requirement, the material CLTE anisotropy is large, and the product is seriously deformed in high-low temperature circulation; or the material is seriously degraded, the physical property of the material is obviously reduced, and the application requirement is not met.
Chinese patent application CN109111699A discloses a PET composite material with high heat conduction and low shrinkage and a preparation method thereof. The ZrW2O7 material in the heat-conducting low-shrinkage filler can effectively reduce the linear expansion coefficient of the PET material and reduce the shrinkage rate of the PET material; and the Al powder particles form a complete net matrix which is connected with each other, and the ZrW2O7 particles are uniformly distributed in the middle of the Al powder in an inlaid manner, so that the structure is favorable for improving the heat conducting performance of the PET composite material, the shrinkage rate is low, and the dimensional stability of the material product is good, so that the material product has great popularization value.
However, the material of the patent has no proper nucleation system and reinforcing system, and can not meet the requirements of the current kitchen appliances and other electrical products needing repeated high and low temperature circulation in the aspects of high temperature resistance, molding processing, material rigidity, CLTE and anisotropy thereof.
In the field of kitchen appliances, such as air fryers, electric ovens, frying pans and the like, many products need to be used alternately in a high-low temperature process due to the need of cooking and heating, but no obvious dimensional change can occur in the use process, otherwise, the products can be deformed and cracked seriously.
Therefore, a new scheme is needed to prepare more excellent heat resistance, CLTE and anisotropy thereof so as to meet the cold and hot alternating use conditions required by kitchen appliances.
Disclosure of Invention
The invention aims to provide a preparation method of a reinforced PET material with high heat resistance and low linear thermal expansion coefficient and a product thereof, so as to overcome the defects of the prior art.
In order to achieve the technical effects, the invention adopts the following technical scheme:
A reinforced PET material having a high heat resistance and a low Coefficient of Linear Thermal Expansion (CLTE), comprising the following components in parts by weight: 100 parts of PET resin, 45-65 parts of glass fiber, 10-25 parts of filling powder, 0.6-2 parts of self-made nucleating agent, 2-4 parts of nucleating accelerator, 1.8 parts of organic wax, 0.8 part of primary antioxidant, 0.4 part of auxiliary antioxidant and 3.8 parts of toughening agent.
In a preferred embodiment, the reinforced PET material comprises the following components in parts by weight: 100 parts of PET resin, 50-60 parts of glass fiber, 15-20 parts of filling powder, 1-1.6 parts of self-made nucleating agent, 2.5-3.5 parts of nucleating accelerator, 1.8 parts of organic wax, 0.8 part of primary antioxidant, 0.4 part of auxiliary antioxidant and 3.8 parts of toughening agent.
In a specific embodiment, the reinforced PET material having a high heat resistance and a low coefficient of linear thermal expansion is characterized in that the PET resin is selected from any one or a combination of fiber-grade slices or film-grade slices having a characteristic viscosity of 0.63 to 0.68 dl/g.
In a specific embodiment, the reinforced PET material with high heat resistance and low linear thermal expansion coefficient is characterized in that the glass fiber is PET and PBT polyester special glass fiber; preferably, the glass fiber is a polyester-dedicated chopped glass fiber.
In a specific embodiment, the reinforced PET material with high heat resistance and low linear thermal expansion coefficient is characterized in that the filler powder is any one or combination of talcum powder and mica; preferably, the talcum powder is coarse flake talcum powder with high length-diameter ratio.
In a specific embodiment, the reinforced PET material with high heat resistance and low linear thermal expansion coefficient is characterized in that the self-made nucleating agent is a compound prepared by reactive extrusion. The self-made nucleating agent comprises the following raw materials in proportion: ethylene acrylate copolymer AC-540A, inorganic nucleating agent Nanomer 1.24TL, organic nucleating agent surlyn 8920, three components with the proportion of 2:33:65. The extrusion temperature of the reactive double-screw extruder is 180-220 ℃, and the screw rotating speed is 300r/min.
In a specific embodiment, the reinforced PET material with high heat resistance and low linear thermal expansion coefficient is characterized in that the nucleating agent promoter is any one or combination of polyethylene glycol, polyethylene glycol dilaurate or powdery solid polyester modifier.
In a specific embodiment, the reinforced PET material with high heat resistance and low linear thermal expansion coefficient is characterized in that the organic wax is any one or combination of a montan wax and a bio-based wax.
In a specific embodiment, the reinforced PET material with high heat resistance and low linear thermal expansion coefficient is characterized in that the primary antioxidant is selected from one or a combination of hindered phenol antioxidants; the auxiliary antioxidant is selected from any one or a combination of phosphite antioxidants; preferably, the primary antioxidant is selected from hindered phenol antioxidants 1010; the auxiliary antioxidant is selected from any one or combination of macromolecular phosphite antioxidants 9228 and 608.
In a specific embodiment, the reinforced PET material with high heat resistance and low linear thermal expansion coefficient is characterized in that the toughening agent is any one or combination of glycidyl ester elastomers.
In a specific embodiment, the preparation method of the reinforced PET material with high heat resistance and low linear thermal expansion coefficient comprises the steps of uniformly mixing the nucleating agent, the nucleation accelerator, the organic wax and the antioxidant, discharging through a main discharging opening, filling powder, discharging glass fiber through double-side feeding, extruding and granulating through a double screw, wherein the thermal deformation temperature of the obtained reinforced PET material reaches 230 ℃, the CLTE in the vertical flow direction is less than 6 multiplied by 10 -5K-1, and the anisotropy of the CLTE is small. The extrusion temperature of the double-screw extruder is 200-240 ℃, and the screw rotating speed is 360-400r/min; preferably, the extrusion temperature of the twin-screw extruder is 220-230 ℃ and the screw rotating speed is 380r/min.
Compared with the prior art, the invention has the following beneficial effects:
The invention combines the advantages of inorganic and organic nucleating agents effectively by adding special self-made nucleating agents into PET, has high crystallization efficiency, does not excessively reduce the physical properties of the material, has excellent dispersibility, can ensure the uniformity of the material, has excellent heat resistance, and can reduce the CLTE and the anisotropy of the material.
According to the invention, the glass fiber and the coarse flake special talcum powder with high length-diameter ratio are added, the coarse flake shape is maintained as much as possible by side feeding in the processing process by means of the special coarse flake shape, and the CLTE and the anisotropism of the material are reduced.
According to the invention, through adding the antioxidant with high-temperature protection and long-acting temperature resistance protection, decomposition and carbonization caused in the processing process are avoided.
The raw materials used in the invention are all in market mass production specifications, the cost performance of the product is high, and the processing is simple and convenient, so that the method is suitable for large-scale industrial production; the whole production process has no obvious solid waste pollution and good environmental protection. The thermal deformation temperature of the reinforced PET material obtained by the invention can reach 230 ℃, the CLTE in the vertical flow direction is less than 6 multiplied by 10 -5K-1, and the anisotropy is small.
In order to make the objects and technical solutions of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with examples of embodiments of the present invention. It will be apparent that the embodiments described are some, but not all embodiments of the invention. All other embodiments, which are made by one of ordinary skill in the art without creative effort, based on the described embodiments of the present invention are within the protection scope of the present invention.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
The PET resin is selected from any one or combination of fiber grade slice or film grade slice with characteristic viscosity of 0.63-0.68 dl/g. The fiber grade slice is, for example, but not limited to, three-lane PET CZ-5011, ceremony PET SB500, etc. The film grade slice is, for example, but not limited to, three-lane PET CZ-302, ceremonious PET FG600, etc.
The glass fiber is PET, but not limited to, but is especially a chopped glass fiber for PBT polyester, such as 534A of a boulder glass fiber, T436W of a Mount Taishan glass fiber, and the like.
The filler powder is any one or combination of talcum powder and mica. The talcum powder is a coarse flake special talcum powder with high length-diameter ratio, such as HAR T84 of beneficial rake, but is not limited to the specific talcum powder.
The self-made nucleating agent is a compound of ethylene acrylic acid copolymer prepared by reactive extrusion, inorganic nucleating agent organic nano montmorillonite and ionic polymer. The ethylene acrylic acid copolymer is, for example, AC-540A of Honival; the organic nano montmorillonite is Nanomer of Nanocor in the United states
1.24TL, DK5 of Zhejiang Feng hong, and the like, but is not limited thereto. The ionic polymer is, for example, surlyn 8920 from DuPont.
The nucleating agent accelerator is any one or combination of polyethylene glycol, polyethylene glycol dilaurate or powdery solid polyester modifier. The polyethylene glycol is exemplified by, but not limited to, sea-safe PEG4000, happy PEG4000, etc. The polyethylene glycol dilaurate may be, for example, but not limited to, PEG400DL of sea-safe petrochemical industry or PEG400DL of the alchox chemical industry. The powdery solid polyester modifier is, for example, GLOBINEX A-51, A-55, etc. of DIC, but not limited thereto.
The organic wax is any one or combination of montan wax or bio-based wax. The montan wax is Licowax OP wax of Clariant, for example. The bio-based wax is Licocare RBW 300,300, 300flakes VITA, for example.
The main antioxidant is selected from one or a combination of hindered phenol antioxidants; the auxiliary antioxidant is selected from any one or a combination of phosphite antioxidants; the primary antioxidant is, for example, hindered phenol antioxidant 1010; the auxiliary antioxidant is, but not limited to, S-9228 of Dufu chemistry, revonox 608,608 of Taiwan Qiti, etc.
The toughening agent is selected from any one or combination of glycidyl ester elastomers; the toughening agent is, for example, AX8900 of Acomax, PTW of DuPont, etc., but is not limited thereto.
The raw materials are uniformly mixed according to a proportion, extruded and granulated by a double-screw extruder, wherein the extrusion temperature of the extruder is 200-240 ℃, and the screw rotating speed is 380r/min.
The invention has the technical characteristics that: since PET has a low crystallization rate due to the rigidity of the molecular chain, and has a low crystallinity and poor heat resistance, it is necessary to improve the crystallinity. After the nucleating agent system and the glass fiber are added into the PET, in the use process of some heated environments, the CLTE and the anisotropy thereof are large, so that the size of the product can be changed under the alternating condition of cold and heat, and the use requirement can not be met, and therefore, the CLTE and the anisotropy thereof are required to be improved. The invention uses self-made nucleating agent prepared by reactive extrusion, and the self-made nucleating agent comprises the following components: ethylene acrylate copolymer AC-540A, inorganic nucleating agent Nanomer 1.24TL, organic nucleating agent surlyn 8920 complex, ratio 2:33:65. The prepared nucleating agent not only keeps high nucleating efficiency, but also reduces PET chain breakage degradation as much as possible, and has good dispersing capability, does not influence the physical properties of the composite material, and has good material uniformity; meanwhile, the special solid powder polyester modifier A-55 is used, so that the movement capability of a molecular chain of PET is improved, the mobility of PET is improved, and the PET is greatly promoted to crystallize by matching with a self-made nucleating agent, so that the PET material with excellent crystallization is obtained. Under the effect of glass fiber reinforcement, the material has excellent heat resistance. The high-length-diameter ratio coarse flake special talcum powder HAR 84 adopted by the invention benefits from the special thin-layer stripping manufacturing process, and the flake index is doubled compared with that of the common talcum powder, so that after HAR 84 is added into a formula system, the CLTE of the composite material is low, and the anisotropy of the composite material is small. The organic wax used in the invention is bio-based wax Licocare RBW 300, 300flakes VITA, and the excellent lubrication and dispersion effect of the organic wax is beneficial, so that the excellent dispersion of glass fiber and HAR T84 in the material in the processing process is ensured.
Under the combined action of the components, the thermal deformation temperature of the reinforced PET material obtained after mixing, extruding and granulating can reach 230 ℃, the CLTE in the vertical flow direction is less than 6 multiplied by 10 -5K-1, and the anisotropy is small.
The invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
The sources of the raw materials used in the following examples are as follows:
| Name of product | Model number | Manufacturing factories |
| PET resin | SB500 | Chemical fibre for instrument sign |
| Glass fiber | 534A | Boulder group |
| Filler powder | HAR T84 | Yirui stone |
| Ethylene acrylic acid copolymer | AC-540A | Honiswell |
| Inorganic nucleating agent | Nanomer 1.24TL | Nanocor |
| Organic nucleating agents | Surlyn 8920 | Dupont |
| Nucleation promoter | A-55 | DIC |
| Lubricant | Licocare RBW 300flakes | Kelaien |
| Antioxidant | 1010 | Basoff' s |
| Antioxidant | 608 | Odd titanium |
| Toughening agent | PTW | Dupont |
The reinforced PET material obtained by double-screw extrusion granulation is tested for relevant performance indexes by adopting the following test method:
tensile strength was tested according to GB/T1040-2006;
Flexural strength and flexural modulus were tested according to GB/T9341-2008;
Notched impact strength was tested according to GB/T1843-2008;
Heat distortion temperature according to GB/T1634-2019 test
CLTE was tested according to GB/T36800.2-2018;
Example 1
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 264A 26Kg of glass fiber, 84 Kg of talcum powder HAR T, 0.4Kg of self-made nucleating agent, 0.4Kg of nucleation accelerator A-55 2Kg of nucleation accelerator A-55 Kg of lubricant Licocare RBW 300 flags 1Kg of antioxidant 1010 0.2Kg of antioxidant 608.4 Kg of toughening agent PTW 2Kg;
Stirring PET, a self-made nucleating agent, a nucleation accelerator, an antioxidant, a lubricant and a toughening agent in a high-speed mixer for 3 minutes, fully and uniformly mixing, and adding the mixture into an extruder through a main feed opening and a feed opening by an automatic metering weightlessness scale; the coarse flaky talcum powder with high length-diameter ratio and the chopped glass fiber are added into a double-screw extruder through automatic weighing weightlessness scales through double-side feeding and side discharging openings. The extrusion temperature of the extruder is 235 ℃, the screw speed of the extruder is 380rpm, and the extruded material strip is subjected to water cooling, granulating and sieving to obtain a sample 1.
Example 2
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 30Kg of glass fiber 534A, 84 Kg of talcum powder HAR T, 0.4Kg of self-made nucleating agent, 0.4Kg of nucleation accelerator A-55 Kg, 1Kg of lubricant Licocare RBW 300 flags, 0.2Kg of antioxidant 1010, 0.4Kg of antioxidant 608 and 2Kg of toughening agent PTW;
Wherein the extrusion temperature of the double-screw extruder is 200 ℃, and the screw rotating speed is 360r/min; the remaining non-described parts are the same as in example 1, and will not be described again, whereby sample 2 can be produced.
Example 3
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 34Kg of glass fiber 534A, 84 Kg of talcum powder HAR T, 0.4Kg of self-made nucleating agent, 0.4Kg of nucleation accelerator A-55 Kg, 1Kg of lubricant Licocare RBW 300 flags, 0.2Kg of antioxidant 1010, 0.4Kg of antioxidant 608 and 2Kg of toughening agent PTW;
Wherein the extrusion temperature of the double-screw extruder is 220 ℃, and the screw rotating speed is 370r/min; the remaining non-described parts are the same as in example 1, and will not be described again, whereby sample 3 can be produced.
Example 4
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 264A 26Kg of glass fiber, 84 Kg of talcum powder HAR T, 0.8Kg of self-made nucleating agent, 1.6Kg of nucleating agent A-55, 1Kg of lubricant Licocare RBW and 300 discs, 0.2Kg of antioxidant 1010, 0.4Kg of antioxidant 608 and 2Kg of toughening agent PTW;
Wherein the extrusion temperature of the double-screw extruder is 240 ℃ and the screw rotating speed is 400r/min; the remaining undescribed portions are the same as in example 1 and are not repeated, whereby sample 4 can be prepared.
Example 5
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 30Kg of glass fiber 534A, 84 Kg of talcum powder HAR T, 0.8Kg of self-made nucleating agent, 1.6Kg of nucleating agent A-55, 1Kg of lubricant Licocare RBW and 300 discs, 0.2Kg of antioxidant 1010, 0.4Kg of antioxidant 608 and 2Kg of toughening agent PTW;
wherein the extrusion temperature of the twin-screw extruder is 230 ℃, and the screw rotating speed is 390r/min. The remaining non-described portions are the same as in example 1, and are not repeated, whereby sample 5 can be produced.
Example 6
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 34Kg of glass fiber 534A, 84 Kg of talcum powder HAR T, 0.8Kg of self-made nucleating agent, 1.6Kg of nucleating agent A-55, 1Kg of lubricant Licocare RBW and 300 discs, 0.2Kg of antioxidant 1010, 0.4Kg of antioxidant 608 and 2Kg of toughening agent PTW;
Wherein the extrusion temperature of the double-screw extruder is 220 ℃, and the screw rotating speed is 380r/min. The remaining undescribed portions are the same as in example 1 and are not repeated, whereby sample 6 can be prepared.
Example 7
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 264A 26Kg of glass fiber, 84 Kg of talcum powder HAR T, 1.1Kg of self-made nucleating agent, 1.3Kg of nucleating agent A-55.3 Kg of nucleating agent A-55 Kg of lubricating agent Licocare RBW, 1010.2 Kg of antioxidant, 608.4 Kg of antioxidant and 2Kg of toughening agent PTW;
Wherein the extrusion temperature of the double-screw extruder is 220 ℃, and the screw rotating speed is 370r/min. The remaining undescribed portions are the same as in example 1 and are not repeated, whereby sample 7 can be prepared.
Example 8
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 30Kg of glass fiber 534A, 84 Kg of talcum powder HAR T, 1.1Kg of self-made nucleating agent, 1.3Kg of nucleating agent A-55.3 Kg of nucleating agent A-55 Kg of lubricating agent Licocare RBW, 1010.2 Kg of antioxidant, 608.4 Kg of antioxidant and 2Kg of toughening agent PTW;
wherein the extrusion temperature of the double-screw extruder is 240 ℃, and the screw rotating speed is 360r/min; the remaining undescribed portions are the same as in example 1 and are not repeated, whereby sample 8 can be prepared.
Example 9
In this embodiment, the weight portions of the raw materials are as follows: 500 Kg of PET SB (polyethylene terephthalate) 500, 34Kg of glass fiber 534A, 84 Kg of talcum powder HAR T, 1.1Kg of self-made nucleating agent, 1.3Kg of nucleating agent A-55.3 Kg of nucleating agent A-55 Kg of lubricating agent Licocare RBW, 1Kg of antioxidant 1010.2 Kg of antioxidant 608.4 Kg of toughening agent PTW 2Kg;
Wherein the extrusion temperature of the double-screw extruder is 240 ℃, and the screw rotating speed is 360r/min. The remaining undescribed portions are the same as in example 1 and are not repeated, whereby sample 9 can be produced.
Comparative example 1
In this embodiment, the weight of each raw material is: PET SB500 54Kg, glass fiber 534A 40Kg, self-made nucleating agent 0.8Kg, nucleation accelerator A-55.6 Kg, lubricant Licocare RBW 300flakes Kg, antioxidant 1010.2 Kg, antioxidant 608 0.4Kg, toughening agent PTW 2Kg;
Wherein the extrusion temperature of the double-screw extruder is 220 ℃, and the screw rotating speed is 380r/min. The other undescribed portions are the same as in example 1, and are not repeated, whereby a comparative example can be produced.
Comparative example 2
In this embodiment, the weight of each raw material is: 500 Kg of PET SB (polyethylene terephthalate) 500, 30Kg of glass fiber 534A, 84 Kg of talcum powder HAR T, 0.4Kg of nucleating agent NAV101, 1.6Kg of nucleating agent A-55, 0.2Kg of antioxidant 1010, 0.4Kg of antioxidant 608, 1Kg of lubricant Licocare RBW 300flakes and 2Kg of toughening agent PTW;
Wherein the extrusion temperature of the twin-screw extruder is 230 ℃, and the screw rotating speed is 390r/min. The other undescribed portions are the same as in example 1, and are not repeated, whereby a comparative example can be produced.
The raw material compositions (parts by weight) of the comparative examples of the respective examples are shown in Table 1.
TABLE 1
Performance tests were conducted on examples and comparative examples, respectively, and the test results are shown in Table 2.
Table 2 table of performance data for examples and comparative examples
From the above results, it is clear that, compared with comparative example 1, examples 1,2 and 3 have low heat distortion temperature due to insufficient addition amount of the nucleating agent, insufficient nucleation efficiency during molding and cooling, low crystallization speed of the material and low crystallinity; examples 7,8 and 9 have low mechanical properties due to degradation of the material caused by excessive addition of the nucleating agent; as shown in examples 4,5 and 6, the reinforced PET material with heat distortion temperature up to 230 ℃, CLTE less than 6×10 -5K-1 in vertical flow direction and small anisotropism can be prepared by preferably preparing nucleating agent, nucleation promoter and coarse flake talcum powder with high length-diameter ratio. Compared with comparative example 2, example 5 has better nucleation effect due to the self-made nucleating agent in the condition of consistent mineral powder filling, glass fiber and the like, and the material has faster crystallization speed and higher crystallinity, and both the heat distortion temperature and the CLTE are superior to those of the material added with the commercially available nucleating agent. Therefore, the embodiments 4,5 and 6 can meet the use of kitchen appliances, and are convenient for large-scale popularization and application.
The embodiments of the present invention have been further described above with reference to specific examples, which are intended to be illustrative of the present invention and not limiting. The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and are not intended to limit the technical concept and scope of the present invention, and various modifications and improvements made by those skilled in the art should fall within the scope of the present invention without departing from the design concept of the present invention.
Claims (9)
1. The reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof is characterized by comprising the following components in parts by weight: 100 parts of PET resin, 45-65 parts of glass fiber, 10-25 parts of filling powder, 0.6-2 parts of self-made nucleating agent, 2-4 parts of nucleating accelerator, 1.8 parts of organic wax, 0.8 part of primary antioxidant, 0.4 part of auxiliary antioxidant and 3.8 parts of toughening agent.
The self-made nucleating agent is prepared by reactive extrusion, and comprises the following components: ethylene acrylate copolymer AC-540A, inorganic nucleating agent Nanomer 1.24TL, organic nucleating agent surlyn 8920 complex, ratio 2:33:65;
And the self-made nucleating agent also comprises a solid powder polyester modifier A-55, coarse flaky special talcum powder HAR T84 with high length-diameter ratio and bio-based wax.
2. The reinforced PET material having a low coefficient of linear thermal expansion and anisotropy thereof according to claim 1, wherein the PET resin is selected from any one or a combination of a fiber grade slice or a film grade slice having a characteristic viscosity of 0.63 to 0.68 dl/g.
3. The reinforced PET material having a low linear thermal expansion coefficient and anisotropy thereof according to claim 1, wherein the glass fiber is a PET, PBT polyester dedicated glass fiber.
4. The reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof according to claim 1, wherein the filler powder is any one or combination of talcum powder and mica;
The talcum powder is coarse flake talcum powder with high length-diameter ratio.
5. The reinforced PET material of claim 1, wherein the nucleating agent promoter is any one or a combination of polyethylene glycol, polyethylene glycol dilaurate or powdered solid polyester modifiers.
6. The reinforced PET material of claim 1, wherein the organic wax is any one or a combination of a montan wax and a bio-based wax.
7. The reinforced PET material having a low coefficient of linear thermal expansion and anisotropy thereof according to claim 1, wherein the primary antioxidant is selected from one or a combination of hindered phenol antioxidants;
the auxiliary antioxidant is selected from any one or combination of phosphite antioxidants.
8. The reinforced PET material of claim 1, wherein the toughening agent is any one or a combination of glycidyl elastomers.
9. A preparation method of reinforced PET material with low linear thermal expansion coefficient and anisotropy thereof is characterized in that resin, nucleating agent, nucleation accelerator, organic wax and antioxidant according to claims 1-8 are uniformly mixed and fed into a main feed opening, powder is filled, glass fiber is fed and fed from two sides, and is subjected to double-screw extrusion granulation, the extrusion temperature of a double-screw extruder is 200-240 ℃, the screw rotating speed is 360-400r/min, the thermal deformation temperature of the obtained reinforced PET material reaches 230 ℃, the CLTE in the vertical flow direction is less than 6 multiplied by 10 -5K-1, and the anisotropy of the CLTE is small.
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| CN101402784A (en) * | 2008-11-10 | 2009-04-08 | 上海金发科技发展有限公司 | Glass fiber reinforced polyethylene terephthalate composite material and method of producing the same |
| CN110628131A (en) * | 2019-09-26 | 2019-12-31 | 金发科技股份有限公司 | Polypropylene composite material with low shrinkage and low linear expansion coefficient and preparation method thereof |
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| CN101280095A (en) * | 2008-05-20 | 2008-10-08 | 上海大学 | Glass fiber reinforced polyethylene glycol terephthalate composite material and preparation thereof |
| CN101302331B (en) * | 2008-05-21 | 2011-12-07 | 深圳市科聚新材料有限公司 | Poly(trimethylene terephthalate) composite material and preparation thereof |
| CN102002219B (en) * | 2010-11-29 | 2012-10-10 | 中国蓝星（集团）股份有限公司 | Method for improving crystallization property of PTT or PTT/PBT blend |
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| CN110628131A (en) * | 2019-09-26 | 2019-12-31 | 金发科技股份有限公司 | Polypropylene composite material with low shrinkage and low linear expansion coefficient and preparation method thereof |
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