CN110194884A - A kind of high heat resistance resistant to hydrolysis imitates porcelain PBT composite and its preparation method and application - Google Patents
A kind of high heat resistance resistant to hydrolysis imitates porcelain PBT composite and its preparation method and application Download PDFInfo
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- CN110194884A CN110194884A CN201910529573.6A CN201910529573A CN110194884A CN 110194884 A CN110194884 A CN 110194884A CN 201910529573 A CN201910529573 A CN 201910529573A CN 110194884 A CN110194884 A CN 110194884A
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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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- 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
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to modified plastics field, specifically discloses a kind of high heat resistance resistant to hydrolysis and imitate porcelain PBT composite and its preparation method and application.The composite material is made of polybutylene terephthalate (PBT), polyethylene terephthalate, glass, filler, toughener, ester exchange inhibitor, hydrolysis agent, antioxidant and lubricant.The present invention, which is used, influences lesser barium sulfate to PBT glossiness for filler, prepares imitative porcelain PBT composite.And on this basis, glass is added, improves the heat resistance and mechanical strength of imitative porcelain PBT composite;PET is added, improves the glossiness of imitative porcelain PBT composite;Anti-hydrolysis agent is added, improves the hydrolytic Resistance of imitative porcelain PBT composite.Operation of the present invention is simple, and the high heat resistance resistant to hydrolysis of acquisition, which imitates porcelain PBT composite, can solve some defects existing for ceramics, expands and even replaces application of the ceramics on the fields such as daily necessities, kitchen and bath, craftwork, has good market promotion prospect.
Description
Technical field
The invention belongs to modified plastics fields, and in particular to a kind of high heat resistance resistant to hydrolysis imitates porcelain PBT composite and its system
Preparation Method and application.
Background technique
Polybutylene terephthalate (PBT) (PBT), which is that milky is translucent, arrives opaque, crystal type thermoplasticity saturated polyester,
PBT resin with its excellent mechanical property, electrical property, heat resistance, processing performance, especially good comprehensive performance and in electricity
Sub- electric appliance, auto industry and machinery, instrument and meter and household electrical appliance etc. are widely applied in fields.But gather with other
The problem of ester is the same, and PBT is equally existed intolerant to hydrolysis.PBT is usually formed by terephthalic acid (TPA) and 1,4-butanediol dehydrating condensation,
This is a reversible reaction, and under the action of water, PBT may be hydrolyzed, so that strand shortens, the strength of materials is reduced, and is become fragile, very
To cracking, the progress of hydrolysis can be aggravated by increasing temperature.
Ceramics are to be made using natural clay and various natural minerals as primary raw material by crushing to be kneaded, form and calcine
Material various products.In general, Production of Ceramics process includes three bases such as blank manufacture, blank forming, porcelain sintering
This stage.Production of Ceramics process is a kind of production process of procedural style, and continuity is lower, causes its production cycle long.Separately
Outside, the larger (2.7g/cm of ceramic specific gravity3Left and right), and it is very crisp, and this has enough to meet the need it and transport proposes biggish challenge.
PBT composite has the characteristics that design freedom is high, shaping speed is fast, and it is relative to ceramics, density compared with
Gently, toughness is preferable.The exploitation of imitative porcelain PBT composite, can solve some defects existing for ceramics, expands and even replaces ceramics
Application on the fields such as daily necessities, kitchen and bath, craftwork.
Chinese patent application CN 101654542 discloses a kind of high-temperature resistant porcelain imitation material and its production method.Its composition is pressed
According to weight percent meter, including melamine resin 30~35%;Glass 0~10%;Colorant 0~2%;Curing agent
0.5~2%;Auxiliary agent 0.5~3%.The patent preparation process includes resins synthesis, raw material mixing, wet feed drying, grinding screening etc.
Process, process is complicated, and undeclared porcelain imitation material is formed by which kind of mode, is not also said to the performance of material
It is bright.
Chinese patent application CN 101608055 discloses a kind of production method of imitative porcelain carving glue material.It is formed according to weight
Measure percentages, including PBT 27.4%;Barium sulfate 71%;Silane coupling agent 0.6%;Vinyl bis-stearamides 0.3%;Liquid
Body paraffin 0.3%;Antioxidant 1010 0.2%;Irgasfos 168 0.2%, but the patent does not equally carry out the performance of material
Explanation.
Chinese patent application CN102617068 discloses the imitative ceramic PBT composite of one kind and preparation method.It is formed
According to parts by weight, including PBT resin 100, ceramic powder 200~400, coupling agent 1~2, antioxidant 0.5~1, lubricant 1~
2.The material has good impact resistance and surface gloss is high, can inject or be pressed and molded repeatedly, overcome traditional ceramics material
Expect the disadvantages of brittleness, impact resistance can be low, processing technology is single, recycling is complicated.But the patent is not compound to imitative ceramics PBT
The heat resistance and hydrolytic resistance of material can be carried out research.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of high heat resistance water resistant
Solve imitative porcelain PBT composite.The composite material has excellent heat resistance, excellent hydrolytic Resistance, while having design
Freedom degree is high, and the fast feature of shaping speed can substitute ceramics, for fields such as daily necessities, kitchen and bath, craftworks.
Another object of the present invention is to provide the preparation methods that above-mentioned high heat resistance resistant to hydrolysis imitates porcelain PBT composite.
A further object of the present invention is to provide the applications that above-mentioned high heat resistance resistant to hydrolysis imitates porcelain PBT composite.
The object of the invention is achieved through the following technical solutions:
A kind of imitative porcelain PBT composite of high heat resistance resistant to hydrolysis, the composite material is by polybutylene terephthalate (PBT)
(PBT), polyethylene terephthalate (PET), glass (glass fibre), filler, toughener, ester exchange inhibitor, water-fast
Agent, antioxidant and lubricant composition are solved, calculated in weight percent, dosage of each component is as follows:
Preferably, it is as follows to imitate porcelain PBT composite dosage of each component for the high heat resistance resistant to hydrolysis:
Preferably, the PBT, inherent viscosity are 0.8~1.1dl/g.It is too low lower than the PBT molecular weight of 0.8dl/g,
Influence material mechanical performance, although and be higher than 1.1dl/g when mechanical performance be unfavorable for processing due to its poor fluidity.
Preferably, the PET, intrinsic viscosity are 0.6~0.8dl/g.The PET lower than 0.6dl/g points of intrinsic viscosity
Son amount is too low, and material mechanical performance is poor, and intrinsic viscosity is higher than the PET poor fluidity of 0.8dl/g, brings processing difficulties.
Preferably, the glass is alkali-free glass fibre, and 7~17 μm of filament diameter, 3~24mm of chopped length.
Preferably, the filler is barium sulfate, and average grain diameter Dv50 is 0.8 μm~1.2 μm.
Preferably, the toughener is the random ternary polymerization of ethylene-methyl acrylate-glyceryl methacrylate
Object.
Preferably, the ester exchange inhibitor is triphenyl phosphate (TPP) and sodium acid pyrophosphate (SAPP) by any
The compound of ratio.
Preferably, the anti-hydrolysis agent is bisphenol A type epoxy resin, epoxide number 1.0-2.0Eq/Kg.
Preferably, the antioxidant is the compounding antioxidant system that hindered phenol and phosphite ester form in any proportion.
Preferably, the lubricant is silicone powder.
The present invention is added to the lesser barium sulfate filler of glossiness damage ratio, preparation has ceramics using PBT resin as substrate
The imitative porcelain PBT composite of texture expands material application to further increase material property, and the present invention on this basis, adds
Enter other components and advanced optimizes material solution.In order to further increase the glossiness of material, PET resin is added;In order to improve
Glass is added in the heat resistance of material;In order to improve the anti-hydrolytic performance of PBT, hydrolysis agent is added.
It is a kind of prepare above-mentioned high heat resistance resistant to hydrolysis imitate porcelain PBT composite preparation method, include the following steps: by PBT,
Mixing machine mixing is added in PET, glass, filler, toughener, ester exchange inhibitor, anti-hydrolysis agent, antioxidant and lubricant, will mix
Extruder main feeding hopper is added in material after conjunction, by double screw extruder extruding pelletization, high heat resistance resistant to hydrolysis is made and imitates porcelain PBT
Composite material.
Preferably, above-mentioned incorporation time is 3~5min;The revolving speed of double screw extruder is 300~500r/min, and temperature is
220~260 DEG C.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) PET is added, the glossiness of imitative porcelain PBT composite can be significantly improved, reduces barium sulfate and glass addition pair
The influence of PBT composite glossiness;
(2) glass is added, the heat resistance and mechanical strength of imitative porcelain PBT composite can be improved;
(3) anti-hydrolysis agent is added, the hydrolytic Resistance of imitative porcelain PBT composite can be improved, expand it in high temperature and humidity
Under the conditions of application.The present invention is being obviously improved the water-fast of PBT composite as anti-hydrolysis agent using bisphenol A type epoxy resin
While solving performance, the mechanical performance of composite material is not influenced;Additionally there is the advantage in cost, traditional hydrolysis agent is adopted
It is very high with polycarbodiimide price, significantly improving for cost is brought a small amount of addition.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
The embodiment of the present invention and comparative example are molded into the standard batten of test according to standard requirements and are tested.It draws
Stretch test according to ISO527 standard, Izod notched impact strength according to ISO180 standard, heat distortion temperature test according to
ISO75-2 standard (1.8MPa).Hydrolysis testing standard is as follows: (1) 90 DEG C of regulating thermostatic constant humidity cabinet temperature, humidity 90%;(2)
Impact batten is placed in high temperature and humidity case;Batten is taken out after (3) 1000 hours, is placed in 23 DEG C, the culture of humidity 50%
Izod notched impact strength test is carried out in case after 24 hours, 5 battens of each condition test are simultaneously tied with average value for test
Fruit, and calculate percentage of the Izod notched impact strength relative to initial tensile strength.Glossiness is tested according to ASTM
D523, using 60 ° of angles.
The raw material used in the embodiment of the present invention and comparative example is as follows:
PBT:PBT1100A, (intrinsic viscosity 1.0dL/g), Xingchen Synthetic Matrials Co., Ltd., Nantong;
PET: superbright light polyester slice (intrinsic viscosity 0.68dL/g), Jiangsu Hengli Chemical Fibre Co., Ltd.;
Barium sulfate: 20211, Hunan (new to shake) fine chemistry Co., Ltd;
Talcum powder: HTP05L (11000 mesh), Italian Yi meter Fa ratio (Imifabi) company;
Glass EC13-4.5-536S: 13 μm of filament diameter, chopped length 4.5mm, the limited public affairs of tai shan glass fibre
Department;
Toughener: AX8900, French A Kema (Arkema) company;
Ester exchange inhibitor: TPP, Zhejiang Wansheng Co., Ltd., SAPP, Shifang City Zhi Xin Chemical Co., Ltd.;
Anti-hydrolysis agent: Araldite GT-7072 (1.68~1.75Eq/Kg of epoxide number), U.S.'s Hensel step (Huntsman)
Company;
Antioxidant: hindered phenol 1010, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, Germany
BASF (Basf) company;Phosphite ester S-9228 (bis- (2,4-two cruel bases) pentaerythritol diphosphites), the U.S.'s all good fortune
(Dover) company;
Lubricant: silicone powder TEGOMER E525, German Degussa (Degussa AG) company.
Embodiment 1
A kind of high heat resistance resistant to hydrolysis imitates the preparation method of porcelain PBT composite, comprising the following steps:
(1) by PBT, PET, glass, filler, toughener, ester exchange inhibitor, anti-hydrolysis agent, antioxidant and lubrication in table 1
The amount of agent weighs raw material;
(2) various raw materials are mixed into mixing machine 5min, extruder main feeding hopper is then added, passes through twin-screw extrusion
Machine extruding pelletization.
The revolving speed of double screw extruder is 300r/min, and temperature is 220~260 DEG C.Resulting high heat resistance resistant to hydrolysis imitates porcelain
PBT composite performance is shown in Table 2.
Embodiment 2
A kind of high heat resistance resistant to hydrolysis imitates the preparation method of porcelain PBT composite, comprising the following steps:
(1) by PBT, PET, glass, filler, toughener, ester exchange inhibitor, anti-hydrolysis agent, antioxidant and lubrication in table 1
The amount of agent weighs raw material;
(2) various raw materials are mixed into mixing machine 3min, extruder main feeding hopper is then added, passes through twin-screw extrusion
Machine extruding pelletization.
The revolving speed of double screw extruder is 500r/min, and temperature is 220~260 DEG C.Resulting high heat resistance resistant to hydrolysis imitates porcelain
PBT composite performance is shown in Table 2.
Embodiment 3~4
After embodiment 3~4 weighs raw material by table 1 respectively, it is imitative that high heat resistance resistant to hydrolysis is prepared according to the method for embodiment 1
Porcelain PBT composite, resulting high heat resistance resistant to hydrolysis imitate porcelain PBT composite performance and are shown in Table 2.
Comparative example 1~5
After comparative example 1~5 weighs raw material according to table 3 respectively, it is compound that modified PBT is prepared according to the method for embodiment 1
Material.Resulting modified PBT composite material detection is shown in Table 4.
1 high heat resistance resistant to hydrolysis of table imitates the composition of porcelain PBT composite
2 embodiment performance detection of table
The composition of 3 comparative example PBT composite of table
4 comparative example performance detection of table
It can be seen that compared with embodiment 1 by comparative example 1 and barium sulfate be changed to talcum powder, the light of PBT composite
Clearly, impact strength also has a degree of decline for damp degree decline.This is because barium sulfate is ball filler, luminous energy is risen
To good reflex, while and resin combination it is also more preferable.
Compared by comparative example 2 and embodiment 1 as can be seen that the addition of glass can significantly improve PBT composite
Heat distortion temperature and tensile strength.
By comparative example 3 and embodiment 2, comparative example 4 can be seen that anti-hydrolysis agent GT-7072's compared with embodiment 3
The anti-hydrolytic performance of PBT composite can be obviously improved by being added, and with the increase of its content, PBT composite it is resistance to
Hydrolysis property is further promoted.The epoxy-functional of GT-7072 can be reacted with PBT carboxyl end group, play the role of sealing end, be reduced
PBT content of carboxyl end group, to reduce since carboxyl end group provides acid condition catalysis PBT hydrolysis.In addition, bisphenol A type epoxy resin
Other performances such as mechanical performance are influenced little.
By the comparison of comparative example 5 and embodiment 4 as can be seen that the addition of PET resin can improve PBT composite
Glossiness, this is because the addition of PET can inhibit the crystallization of PBT, thus flow PBT can preferably in die cavity, it is right
Glass and filler cladding are more preferable, and product is made to embody higher glossiness.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of high heat resistance resistant to hydrolysis imitates porcelain PBT composite, which is characterized in that the composite material by PBT, PET, glass,
Filler, toughener, ester exchange inhibitor, hydrolysis agent, antioxidant and lubricant composition, calculated in weight percent, each component
Dosage is as follows:
Wherein, the anti-hydrolysis agent is bisphenol A type epoxy resin, epoxide number 1.0-2.0Eq/Kg;The filler is barium sulfate.
2. a kind of high heat resistance resistant to hydrolysis according to claim 1 imitates porcelain PBT composite, which is characterized in that described
PBT, inherent viscosity are 0.8~1.1dl/g.
3. a kind of high heat resistance resistant to hydrolysis according to claim 1 imitates porcelain PBT composite, which is characterized in that described
PET, intrinsic viscosity are 0.6~0.8dl/g.
4. a kind of high heat resistance resistant to hydrolysis according to claim 1 imitates porcelain PBT composite, which is characterized in that the glass
For alkali-free glass fibre, and 7~17 μm of filament diameter, 3~24mm of chopped length.
5. a kind of high heat resistance resistant to hydrolysis according to claim 1 imitates porcelain PBT composite, which is characterized in that the sulfuric acid
Barium average grain diameter Dv50 is 0.8 μm~1.2 μm.
6. a kind of high heat resistance resistant to hydrolysis according to claim 1 imitates porcelain PBT composite, which is characterized in that the toughening
Agent is ethylene-methyl acrylate-glycidyl methacrylate random terpolymer.
7. a kind of high heat resistance resistant to hydrolysis according to claim 1 imitates porcelain PBT composite, which is characterized in that the ester
Exchanger inhibitor is triphenyl phosphate and the compound of sodium acid pyrophosphate in any proportion.
8. a kind of high heat resistance resistant to hydrolysis according to claim 1 imitates porcelain PBT composite, the antioxidant is hindered phenol
With the compounding antioxidant system of phosphite ester composition, lubricant is silicone powder.
9. a kind of described in any item preparation methods of the imitative porcelain PBT composite of high heat resistance resistant to hydrolysis of claim 1 to 8, special
Sign is, include the following steps: by weight percentage, by 20~50%PBT, 10~25%PET, 5~10% glasses, 20~
40% filler, 2~6% toughener, 0.2~0.8% ester exchange inhibitor, 0.5~2% anti-hydrolysis agent, 0.4~0.6% antioxygen
Mixed material is added extruder main feeding hopper, is squeezed by twin-screw by agent and 0.4~0.6% 3~5min of mix lubricant
Machine extruding pelletization out is made high heat resistance resistant to hydrolysis and imitates porcelain PBT composite;The revolving speed of the double screw extruder be 300~
500r/min, temperature are 220~260 DEG C.
10. a kind of described in any item high heat resistance resistant to hydrolysis of claim 1 to 8 imitate porcelain PBT composite in daily necessities, Chu Weihe
Application in field of artware.
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CN111073226A (en) * | 2019-12-18 | 2020-04-28 | 广州市聚赛龙工程塑料股份有限公司 | High-strength high-gloss low-warpage PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof |
CN115850868A (en) * | 2022-12-15 | 2023-03-28 | 东莞市创之润新材料有限公司 | Preparation method of ceramic-like alloy |
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CN115850868A (en) * | 2022-12-15 | 2023-03-28 | 东莞市创之润新材料有限公司 | Preparation method of ceramic-like alloy |
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