CN103923442A - High-temperature-resistant thermal aging basalt fiber-reinforced PBT (Polybutylene Terephthalate) composite material and preparation method thereof - Google Patents
High-temperature-resistant thermal aging basalt fiber-reinforced PBT (Polybutylene Terephthalate) composite material and preparation method thereof Download PDFInfo
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- CN103923442A CN103923442A CN201410157720.9A CN201410157720A CN103923442A CN 103923442 A CN103923442 A CN 103923442A CN 201410157720 A CN201410157720 A CN 201410157720A CN 103923442 A CN103923442 A CN 103923442A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92838—Raw material pre-treatment, e.g. drying or cleaning
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Abstract
The invention discloses a high-temperature-resistant thermal aging basalt fiber-reinforced PBT (Polybutylene Terephthalate) composite material and a preparation method thereof and belongs to the technical field of high molecular materials. The high-temperature-resistant thermal aging basalt fiber-reinforced PBT composite material comprises the following components in percentage by weight: 35-75% of PBT, 20-45% of purpose-made basalt fiber, 3-12% of toughener, 0.2-2.5% of interface modifier, 0.2-2.5% of coupling agent, 0.4-2.0% of antioxidant and 10.3-2.0% of lubricant, wherein surface wetting treatment is performed on the purpose-made basalt fiber by use of a special wetting agent for basalt fiber polyester. Compared with glass fiber-reinforced PBT composite material, the composite material disclosed by the invention has the characteristics of high temperature resistance and obvious thermal aging performance, and still keeps excellent impact toughness and mechanical performance after being subjected to a long-term high-temperature thermal aging test.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly the aging basalt fibre of a kind of high temperature heat-resistant strengthens polybutylene terephthalate matrix material and preparation method thereof.
Background technology
Polybutylene terephthalate (hereinafter to be referred as PBT) is a kind of thermoplastic engineering plastic of high comprehensive performance, there is good electrical insulation capability and chemical solvent resistance energy, crystallization rapidly at a lower temperature simultaneously, so moulding processability is good, shaping cycle is short, be applicable to the product for manufacturing structure complexity, be widely used in the fields such as electric and machinofacture, as micromachine housing etc.
In order to improve physical strength and to reduce molding shrinkage, manufacturer adopts glass fibre to carry out modification preparation enhancing PBT matrix material as toughener conventionally, to meet electric and other industry requirement.Along with the fast development of microelectronics information technology, electronic devices and components present miniaturization, integrated and modular development trend, correspondingly the electric structured materials such as PBT are proposed to requirements at the higher level, as physical strength of better high temperature heat-resistant aging resistance and Geng Gao etc.General fiber glass reinforced PBT matrix material cannot meet above service requirements.
Mineral fibre is as main modification starting material, and its kind selection and performance have determined the over-all properties of PBT matrix material.Basalt is the natural product of volcanicity, and mineralogical composition is purer than glass.The cooling rear glass of melting forms non-crystalline solids, and basalt still has crystalline structure, so the tensile modulus of basalt fibre, shock resistance and high low-temperature stability are much better than glass fibre.
Existing publication CN101230193A mentions basalt fibre and is used for preparing the method for Reinforced Nylon composition, and every mechanical property and the thermotolerance of basalt fibre reinforced nylon composition all have raising by a relatively large margin.Yet there are no relevant report and research that basalt fibre should be used for preparing PBT matrix material, also have no Patents report.Therefore developing a kind of basalt fibre with high temperature heat-resistant aging resistance excellence, to strengthen polybutylene terephthalate matrix material necessary.
Basalt fibre in the market can not effectively solve the surface bonding problem of basalt fibre and PBT resin, and key is that the surface infiltration processing of basalt fibre exists technological difficulties, and the domestic research to basalt fibre sizing agent special is less.
Summary of the invention
For overcoming the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide the aging basalt fibre of a kind of high temperature heat-resistant to strengthen polybutylene terephthalate matrix material.Matrix material of the present invention has the exsertile feature of high temperature heat-resistant aging, still keeps excellent impelling strength and mechanical property after long term high temperature heat ageing test.
Another object of the present invention is to provide the aging basalt fibre of above-mentioned high temperature heat-resistant to strengthen the preparation method of polybutylene terephthalate matrix material.
A further object of the present invention is to provide the aging basalt fibre of above-mentioned high temperature heat-resistant to strengthen the application of polybutylene terephthalate matrix material.
The present invention is achieved through the following technical solutions above-mentioned purpose: the aging basalt fibre of a kind of high temperature heat-resistant strengthens polybutylene terephthalate matrix material, be made up of PBT resin, special basalt fibre, toughner, interface modifier, coupling agent, oxidation inhibitor and lubricant I, its composition is as follows by weight ratio:
In order to use basalt fibre polyester sizing agent special to carry out surface infiltration processing, (infiltration temperature is 40 DEG C to described special basalt fibre, infiltrating time is 2 seconds, and in special basalt fibre, polyester sizing agent special content is 0.65%～0.95%) the rear basalt fibre obtaining.
Described special basalt fibre is continuous basalt fiber, and Fibre diameter is 8～15 microns, preferably the basalt continuous fiber of 13 microns.
Described basalt fibre polyester sizing agent special is made up of ternary copolymer emulsion, high molecular weight bisphenol A type polyester emulsion, tensio-active agent, silane coupling agent, lubricant II, ethanol and softening water, and its composition is as follows by weight ratio:
Described ternary copolymer emulsion is the copolymer emulsion system of ethyl propenoate-butyl acrylate-glycidyl methacrylate, is prepared by the component that comprises following weight proportion:
Described ternary copolymer emulsion adopts letex polymerization; its concrete preparation method is as follows: water, ethyl propenoate, butyl acrylate, glycidyl methacrylate, sodium laurylsulfonate, di-isopropylbenzene hydroperoxide, rongalite and V-Brite B are joined respectively in four-hole reactor; under nitrogen protection; temperature of reaction is controlled at 35 DEG C～55 DEG C, reacts and obtains ternary copolymer emulsion after 3～6 hours.
Described high molecular weight bisphenol A type polyester emulsion is preferably the TH960 of Nantong Tianhe Resin Co., Ltd..
Described tensio-active agent is preferably the one in cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride.
Described silane coupling agent is preferably γ-(2,3 glycidoxy) propyl trimethoxy silicane.
Described lubricant II is preferably pentaerythritol stearate.
The preparation method of described basalt fibre polyester sizing agent special is as follows:
A, get ternary copolymer emulsion, high molecular weight bisphenol A type polyester emulsion, tensio-active agent, silane coupling agent, lubricant II, ethanol and softening water by formulation weight score another name;
B, softening water is joined in mixing kettle, open stirrer.The diluent (tensio-active agent and temperature are that the hot water of 50 DEG C dilutes according to volume ratio 1:15) that slowly adds tensio-active agent, stirs 5 minutes, adds silane coupling agent, stirs 3 minutes;
C, add high molecular weight bisphenol A type polyester emulsion, stir 6 minutes;
D, add ternary copolymer emulsion, stir 10 minutes;
E, add the diluent (lubricant II and ethanol are according to weight ratio 1:10 dissolved dilution) of lubricant II, continue to stir after 5 minutes and obtain basalt fibre polyester sizing agent special.
Described PBT resin is the resin of limiting viscosity between 0.6～1.0dl/g, the PBT resin of preferred characteristics viscosity 0.8dl/g.
Described toughner is one or both of ethylene-methyl acrylate-glyceryl methacrylate random terpolymer and high density polyethylene(HDPE), optimal ethylene-methyl acrylate-glycidyl methacrylate random terpolymer.
Described interface modifier is the small molecules epoxy organic compound that contains phenyl ring and the stronger Racemic glycidol ester bond of polarity; Preferably one or both in terephthalic acid diglycidyl ester, tetrahydrophthalic acid bisglycidyl ester and hexahydrophthalic acid bisglycidyl ester.
Described coupling agent is the low molecule silicoorganic compound that contain trimethoxy and have two kinds of different chemical character functional groups, preferably one or both in γ-(methacryloxy) propyl trimethoxy silicane and γ-(2,3 glycidoxy) propyl trimethoxy silicane.
Described oxidation inhibitor is one or both in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester and four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Described lubricant I is one or both in fatty ester amides lubricant and carboxylic ester series lubricant agent; Preferably one or both in ethylene bis-fatty acid amides and pentaerythritol stearate.
The aging basalt fibre of described high temperature heat-resistant strengthens the preparation method of polybutylene terephthalate matrix material, and step is as follows:
1) by formulation weight than having weighed PBT resin, special basalt fibre, toughner, interface modifier, coupling agent, oxidation inhibitor and lubricant I;
2) PBT resin, interface modifier and coupling agent are joined to high-speed mixer (rotating speed is 475RPM), mix 30 seconds;
3) add toughner, oxidation inhibitor and lubricant I, continue to mix 60 seconds;
4) raw material mixing is joined in twin screw extruder, special basalt fibre adds by adding fine mouthful, and 220 DEG C～260 DEG C melt extrude, and cooling and dicing obtains matrix material.
In the electronic and electric components that the aging basalt fibre enhancing of described high temperature heat-resistant polybutylene terephthalate matrix material requires at long term high temperature Working environment and machinofacture parts, apply.
The aging evaluation method of high temperature heat-resistant that the aging basalt fibre of described high temperature heat-resistant strengthens polybutylene terephthalate matrix material is as follows: a, matrix material are dried injection moulding after 6 hours and prepare iso standard test bars in 120 DEG C of air dry ovens; B, with reference to U.S. UL746B standard, standard testing batten is placed in high-accuracy climatic chamber to 160 DEG C of test temperatures, 2000 hours test periods; C, test before high Hygrothermal Aging respectively and high Hygrothermal Aging after tensile strength, modulus in flexure, breach simple beam impact strength and the non-notch simple beam impact strength of batten, calculate the performance retention rate of material after high Hygrothermal Aging.
The principle of the invention is as follows:
Due to polybutylene terephthalate chemical polarity than nylon a little less than, only adopt the modification technology of part silane coupling agent or epoxy chainextender, cannot obviously improve the interface binding intensity between basalt fibre and PBT matrix resin.The conventional content that strengthens basalt fibre in PBT more than 25%, therefore only has by the surface infiltration processing of basalt fibre and could solve well consistency and the interfacial adhesion problem between basalt fibre and PBT matrix resin.
The present invention is directed to the feature of PBT resin terminal hydroxyl and basalt fibre surface tissue, from the design of the consistency of ester group and the chemical reaction characteristic of epoxy group(ing) with prepared a kind of basalt fibre polyester sizing agent special.First adopt emulsion polymerisation process to synthesize the ternary copolymer emulsion of ethyl propenoate-butyl acrylate-glycidyl methacrylate.Then adopt the chemical constitution such as ternary copolymer emulsion and high molecular weight bisphenol A type polyester emulsion, tensio-active agent, silane coupling agent, lubricant II, ethanol and softening water to prepare the basalt fibre polyester sizing agent special that applicable PBT modification is used.
The present invention and basalt fibre manufacturer cooperate, and in basalt fibre wire-drawing shape process, adopt basalt fibre polyester sizing agent special to carry out infiltration modification to its surface.A large amount of epoxide groups and esters of acrylic acid group are contained in special basalt fibre surface by the processing of basalt fibre polyester sizing agent special.Epoxide group is because chemical property is active, is easy under melting situation and the hydroxyl generation chemical reaction of PBT resin, improved the cohesive force of basalt fibre and PBT resin; The ester class of esters of acrylic acid group and PBT resin has close solubility coefficient simultaneously, has improved the consistency of basalt fibre and PBT resin.
The present invention starts with from the surface infiltration technology of basalt fibre, prepare the special basalt fibre that PBT is suitable for, also adopt the composite modified technology of optimization of interface modifier and coupling agent simultaneously, make between PBT resin and basalt fibre, to there is better consistency and interface bond strength, thereby the basalt fibre that obtains high temperature heat-resistant aging resistance excellence strengthens polybutylene terephthalate matrix material, obtains than glass fibre and strengthens the better high temperature heat-resistant aging resistance of PBT matrix material.
As can be seen from the above technical solutions, it is that a kind of basalt fibre polyester sizing agent special of main ingredient carries out surface infiltration processing to basalt fibre that the present invention adopts to make by oneself ternary copolymer emulsion, the lip-deep a large amount of epoxide groups of special basalt fibre are high polar group, chemical property is active, under molten state, be easy to and the hydroxyl reaction of PBT resin end, can significantly improve chemical interactions and interfacial adhesion between basalt fibre and PBT resin; The ester class of the lip-deep esters of acrylic acid group of basalt fibre and PBT resin has close solubility coefficient simultaneously, thereby has improved the consistency of basalt fibre and PBT resin.The collaborative composite modified technology that adopts in addition interface modifier and coupling agent in matrix material preparation process, has further improved consistency and cohesive strength between basalt fibre and PBT resin.
The present invention with respect to advantage and the effect of prior art is:
1, the aging basalt fibre of high temperature heat-resistant that prepared by the present invention strengthens polybutylene terephthalate matrix material and has the exsertile feature of high temperature heat-resistant aging.Compared with glass fiber reinforced polyester mutual-phenenyl two acid bromide two alcohol ester matrix material, matrix material of the present invention still keeps excellent impelling strength and mechanical property after long term high temperature heat ageing test.
2, the aging basalt fibre of high temperature heat-resistant that prepared by the present invention strengthens tensile strength 149MPa, modulus in flexure 8320MPa, the breach simple beam impact strength 12.2kJ/m of PBT matrix material (embodiment 4) before high temperature heat ageing test
2with non-notch simple beam impact strength 53.4kJ/m
2, the glass fibre that above every over-all properties is better than prior art (comparative example 1) strengthens PBT matrix material.
3, the aging basalt fibre of the high temperature heat-resistant that prepared by the present invention strengthen PBT matrix material (embodiment 4) after UL746B standard heat ageing test impelling strength and mechanical property outstanding.Tensile strength 138MPa, modulus in flexure 7750MPa, breach simple beam impact strength 9.7kJ/m
2with non-notch simple beam impact strength 39.5kJ/m
2.Tensile strength thermal ageing retention rate 92.6%, modulus in flexure thermal ageing retention rate 93%, breach simple beam impact strength thermal ageing retention rate 79.5% and non-notch simple beam impact strength thermal ageing retention rate 73.6%, above properties and heat aging performance retention rate strengthen PBT matrix material apparently higher than the glass fibre of prior art (comparative example 1).Particularly the heat aging performance retention rate of breach simple beam impact strength and non-notch simple beam impact strength is respectively than prior art (comparative example 1) high 24.2% and 26.2%.
4, matrix material of the present invention is particularly suitable for manufacturing the electronic and electric components of long term high temperature Working environment requirement, has widened the Application Areas of polybutylene terephthalate matrix material.
Embodiment
Below in conjunction with embodiment and comparative example, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The invention provides the aging basalt fibre of a kind of basalt fibre polyester sizing agent special and a kind of high temperature heat-resistant and strengthen polybutylene terephthalate matrix material.
For ease of the present invention is further understood, now with comparative example, the present invention is described in detail in conjunction with the embodiments.
Ternary copolymer emulsion and the concrete preparation method of basalt fibre polyester sizing agent special and embodiment
Starting material producer and the trade mark that basalt fibre polyester sizing agent special adopts are specific as follows:
The concrete preparation method of ternary copolymer emulsion and embodiment
A, take respectively 200 parts, water by weight ratio, 45 parts of ethyl propenoates, 25 parts of butyl acrylates, 20 parts of glycidyl methacrylate, 3 parts of sodium laurylsulfonates, 0.75 part of di-isopropylbenzene hydroperoxide, 0.5 part of rongalite, 0.25 part of V-Brite B;
B, Jiang Shui, ethyl propenoate, butyl acrylate, glycidyl methacrylate, sodium laurylsulfonate, di-isopropylbenzene hydroperoxide, rongalite and V-Brite B join respectively in four-hole reactor and do not stop to stir;
C, under nitrogen protection, temperature of reaction is controlled at 45 DEG C;
D, reaction obtained ternary copolymer emulsion after 4 hours.
The concrete preparation method of basalt fibre polyester sizing agent special and embodiment
A, take respectively 87.3 parts of 5 parts of ternary copolymer emulsions, 2.5 parts of high molecular weight bisphenol A type polyester emulsions, γ-0.5 part of (2,3 glycidoxy) propyl trimethoxy silicane, 0.4 part of pentaerythritol stearate, 4 parts of ethanol, 0.3 part of cetyl trimethylammonium bromide and softening waters by weight ratio;
B, 82.3 parts of softening waters are joined in mixing kettle, open stirrer.The diluent (the hot water dilutions of 5 parts of temperature 50 Cs of 0.3 part of cetyl trimethylammonium bromide) that slowly adds cetyl trimethylammonium bromide, stirs 5 minutes;
C, add 0.5 part of γ-(2,3 glycidoxy) propyl trimethoxy silicane, stir 3 minutes;
D, add 2.5 parts of high molecular weight bisphenol A type polyester emulsions, stir 6 minutes;
E, add 5 parts of ternary copolymer emulsions, stir 10 minutes;
F, 0.4 part of pentaerythritol stearate obtain basalt fibre polyester sizing agent special with joining continuation stirring in mixing kettle after 4 parts of dissolve with ethanol after 5 minutes.
The aging basalt fibre enhancing concrete preparation method of polybutylene terephthalate matrix material of high temperature heat-resistant and embodiment, comparative example
It is specific as follows that the aging basalt fibre of high temperature heat-resistant strengthens the enforcement of polybutylene terephthalate matrix material starting material producer and the trade mark routine and that comparative example adopts:
Matrix material is implemented example and the concrete preparation method of comparative example
Embodiment 1～6 adopts above-mentioned basalt fibre dedicated polyester treating compound to carry out surface infiltration processing, and (infiltration temperature is 40 DEG C, infiltrating time is 2 seconds, and in special basalt fibre, polyester sizing agent special content is 0.65%～0.95%) after obtain special basalt fibre as strongthener.
Comparative example 1 adopts glass fibre as strongthener.
Comparative example 2 adopts the basalt fibre of 316 models to make (hereinafter to be referred as conventional basalt fibre) for strongthener.
The fibre content of embodiment 1～4, comparative example 1 and comparative example 2 matrix materials is all that the fibre content of 30%, embodiment, 5 matrix materials is that the fibre content of 20%, embodiment, 6 matrix materials is 45%.
Embodiment 1～6 median surface properties-correcting agent is different with coupling agent content and proportioning
Embodiment 1-embodiment 6
Weigh by weight ratio PBT resin and other raw material, PBT resin, interface modifier and coupling agent have been joined to high-speed mixer (rotating speed is 475RPM), mixed 30 seconds; Then toughner, oxidation inhibitor and lubricant I are added and continue to mix 60 seconds.
The raw material mixing is joined in twin screw extruder, and special basalt fibre adds by adding fine mouthful, melt extrudes, and cooling and dicing obtains matrix material.
Forcing machine processing temperature is set to 230 DEG C of district's temperature, two 230 DEG C of district's temperature, three 235 DEG C of district's temperature, four 235 DEG C of district's temperature, five 235 DEG C of district's temperature, six 240 DEG C of district's temperature, seven 240 DEG C of district's temperature, eight 240 DEG C of district's temperature, 245 DEG C of die head temperatures.
Material is dried injection moulding after 6 hours and prepares test bars in 120 DEG C of air dry ovens.
Comparative example 1
Weigh by weight ratio PBT resin and other raw material, PBT resin, interface modifier and coupling agent have been joined to high-speed mixer (rotating speed is 475RPM), mixed 30 seconds; Then toughner, oxidation inhibitor and lubricant I are added and continue to mix 60 seconds.
The raw material mixing is joined in twin screw extruder, and glass fibre adds by adding fine mouthful, melt extrudes, and cooling and dicing obtains matrix material.
Forcing machine processing temperature is set to 230 DEG C of district's temperature, two 230 DEG C of district's temperature, three 235 DEG C of district's temperature, four 235 DEG C of district's temperature, five 235 DEG C of district's temperature, six 240 DEG C of district's temperature, seven 240 DEG C of district's temperature, eight 240 DEG C of district's temperature, 245 DEG C of die head temperatures.
Material is dried injection moulding after 6 hours and prepares test bars in 120 DEG C of air dry ovens.
Comparative example 2
Weigh by weight ratio PBT resin and other raw material, PBT resin, interface modifier and coupling agent have been joined to high-speed mixer (rotating speed is 475RPM), mixed 30 seconds; Then toughner, oxidation inhibitor and lubricant I are added and continue to mix 60 seconds.
The raw material mixing is joined in twin screw extruder, and conventional basalt fibre adds by adding fine mouthful, melt extrudes, and cooling and dicing obtains matrix material.
Forcing machine processing temperature is set to 230 DEG C of district's temperature, two 230 DEG C of district's temperature, three 235 DEG C of district's temperature, four 235 DEG C of district's temperature, five 235 DEG C of district's temperature, six 240 DEG C of district's temperature, seven 240 DEG C of district's temperature, eight 240 DEG C of district's temperature, 245 DEG C of die head temperatures.
Material is dried injection moulding after 6 hours and prepares test bars in 120 DEG C of air dry ovens.
The add-on of embodiment 1～embodiment 6 and comparative example 1, comparative example 2 each compositions is as shown in table 1.
The composite material test result that embodiment 1～embodiment 6 and comparative example 1, comparative example 2 obtain is as shown in table 2.
Table 1 embodiment 1～embodiment 6 and comparative example 1, comparative example 2 specifically fill a prescription (unit be kilogram)
The composite material test result that table 2 embodiment 1～embodiment 6 and comparative example 1, comparative example 2 obtain
Tensile strength is according to ISO527 standard testing.
Modulus in flexure is according to ISO178 standard testing.
Breach simple beam impact strength and non-notch simple beam impact strength are according to ISO179 standard testing.
The aging evaluation method of high temperature heat-resistant, with reference to UL746B standard, is placed on standard testing batten in high-accuracy climatic chamber, 160 DEG C of test temperatures, 2000 hours test periods.Test respectively before high Hygrothermal Aging and high Hygrothermal Aging after tensile strength, modulus in flexure, breach simple beam impact strength and the non-notch simple beam impact strength of batten, calculate the performance retention rate of material after high Hygrothermal Aging.
Performance before performance/high Hygrothermal Aging after performance retention rate=high Hygrothermal Aging.
Embodiment 4(basalt fibre strengthens PBT matrix material) tensile strength 149MPa, modulus in flexure 8320MPa, breach simple beam impact strength 12.2kJ/m before high temperature heat ageing test
2with non-notch simple beam impact strength 53.6kJ/m
2, above every over-all properties is better than comparative example 1(glass fibre and strengthens PBT matrix material).
Embodiment 4(basalt fibre strengthens PBT matrix material) impelling strength and mechanical property after UL746B standard heat ageing test be outstanding.Tensile strength 138MPa, modulus in flexure 7750MPa, breach simple beam impact strength 9.7kJ/m
2with non-notch simple beam impact strength 39.5kJ/m
2.Tensile strength thermal ageing retention rate 92.6%, modulus in flexure thermal ageing retention rate 93%, breach simple beam impact strength thermal ageing retention rate 79.5% and non-notch simple beam impact strength thermal ageing retention rate 73.6%, above properties and heat aging performance retention rate strengthen PBT matrix material apparently higher than comparative example 1(glass fibre).Particularly the heat aging performance retention rate of breach simple beam impact strength and non-notch simple beam impact strength is respectively than comparative example 1 high 24.2% and 26.2%.Embodiment 6 forming process are slightly poorer than embodiment 4.
Draw to draw a conclusion from the test data of embodiment and comparative example: adopt tensile strength, breach simple beam impact strength and the non-notch simple beam impact strength performance of enhancing PBT matrix material prepared by the special basalt fibre of a kind of basalt fibre polyester sizing agent special surface-treated to be better than glass fibre and strengthen PBT matrix material, particularly high Hygrothermal Aging over-all properties is outstanding, and wherein the thermal ageing retention rate of breach simple beam impact strength and non-notch simple beam impact strength is more excellent.Adopt the composite modified technology of interface modifier and coupling agent can obviously improve the interfacial adhesion strength between basalt fibre and PBT resin simultaneously, thereby further improve the over-all properties of basalt fibre enhancing polybutylene terephthalate matrix material.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. the aging basalt fibre of high temperature heat-resistant strengthens polybutylene terephthalate matrix material, it is characterized in that: the aging basalt fibre of described high temperature heat-resistant strengthens polybutylene terephthalate matrix material and is made up of PBT resin, special basalt fibre, toughner, interface modifier, coupling agent, oxidation inhibitor and lubricant I, and its composition is as follows by weight ratio:
Described special basalt fibre is to use basalt fibre polyester sizing agent special to carry out the basalt fibre obtaining after surface infiltration is processed, infiltration temperature used is 40 DEG C, infiltrating time is 2 seconds, and in special basalt fibre, polyester sizing agent special content is 0.65%～0.95%.
2. the aging basalt fibre of high temperature heat-resistant according to claim 1 strengthens polybutylene terephthalate matrix material, it is characterized in that: described basalt fibre polyester sizing agent special is made up of ternary copolymer emulsion, high molecular weight bisphenol A type polyester emulsion, tensio-active agent, silane coupling agent, lubricant II, ethanol and softening water, its composition is as follows by weight ratio:
3. the aging basalt fibre of high temperature heat-resistant according to claim 2 strengthens polybutylene terephthalate matrix material, it is characterized in that: the copolymer emulsion system that described ternary copolymer emulsion is ethyl propenoate-butyl acrylate-glycidyl methacrylate, by being prepared by the component that comprises following weight proportion:
4. the aging basalt fibre of high temperature heat-resistant according to claim 3 strengthens polybutylene terephthalate matrix material, it is characterized in that: described ternary copolymer emulsion adopts letex polymerization, its concrete preparation method is as follows: by water, ethyl propenoate, butyl acrylate, glycidyl methacrylate, sodium laurylsulfonate, di-isopropylbenzene hydroperoxide, rongalite and V-Brite B join respectively in four-hole reactor, under nitrogen protection, temperature of reaction is controlled at 35 DEG C～55 DEG C, react and obtain ternary copolymer emulsion after 3～6 hours.
5. the aging basalt fibre of high temperature heat-resistant according to claim 2 strengthens polybutylene terephthalate matrix material, it is characterized in that:
The TH960 that described high molecular weight bisphenol A type polyester emulsion is Nantong Tianhe Resin Co., Ltd.;
Described tensio-active agent is the one in cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride;
Described silane coupling agent is γ-(2,3 glycidoxy) propyl trimethoxy silicane;
Described lubricant II is pentaerythritol stearate.
6. the aging basalt fibre of high temperature heat-resistant according to claim 2 strengthens polybutylene terephthalate matrix material, it is characterized in that: the preparation method of described basalt fibre polyester sizing agent special is as follows:
A, get ternary copolymer emulsion, high molecular weight bisphenol A type polyester emulsion, tensio-active agent, silane coupling agent, lubricant II, ethanol and softening water by formulation weight score another name;
B, softening water is joined in mixing kettle, open stirrer; Slowly add the diluent of tensio-active agent, stir 5 minutes, add silane coupling agent, stir 3 minutes; The diluent of described tensio-active agent is that tensio-active agent and temperature are that the hot water of 50 DEG C dilutes according to volume ratio 1:15;
C, add high molecular weight bisphenol A type polyester emulsion, stir 6 minutes;
D, add ternary copolymer emulsion, stir 10 minutes;
E, add the diluent of lubricant II, continue to stir after 5 minutes and obtain basalt fibre polyester sizing agent special; The diluent of described lubricant II is that lubricant II and ethanol are according to weight ratio 1:10 dissolved dilution.
7. the aging basalt fibre of high temperature heat-resistant according to claim 1 strengthens polybutylene terephthalate matrix material, it is characterized in that:
Described special basalt fibre is continuous basalt fiber, and Fibre diameter is 8～15 microns;
Described PBT resin is the resin of limiting viscosity between 0.6～1.0dl/g;
Described toughner is one or both of ethylene-methyl acrylate-glyceryl methacrylate random terpolymer and high density polyethylene(HDPE);
Described interface modifier is the small molecules epoxy organic compound that contains phenyl ring and the stronger Racemic glycidol ester bond of polarity;
Described coupling agent is the low molecule silicoorganic compound that contain trimethoxy and have two kinds of different chemical character functional groups;
Described oxidation inhibitor is one or both in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester and four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described lubricant I is one or both in fatty ester amides lubricant and carboxylic ester series lubricant agent.
8. the aging basalt fibre of high temperature heat-resistant according to claim 1 strengthens polybutylene terephthalate matrix material, it is characterized in that: described special basalt fibre is that Fibre diameter is the basalt continuous fiber of 13 microns;
Described PBT resin is the PBT resin of limiting viscosity 0.8dl/g;
Described toughner is ethylene-methyl acrylate-glyceryl methacrylate random terpolymer;
Described interface modifier is one or both in terephthalic acid diglycidyl ester, tetrahydrophthalic acid bisglycidyl ester and hexahydrophthalic acid bisglycidyl ester;
Described coupling agent is one or both in γ-(methacryloxy) propyl trimethoxy silicane and γ-(2,3 glycidoxy) propyl trimethoxy silicane;
Described oxidation inhibitor is one or both in tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester and four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester;
Described lubricant I is one or both in ethylene bis-fatty acid amides and pentaerythritol stearate.
9. the aging basalt fibre of the high temperature heat-resistant described in claim 1～8 any one strengthens the preparation method of polybutylene terephthalate matrix material, it is characterized in that step is as follows:
1) by formulation weight than having weighed PBT resin, special basalt fibre, toughner, interface modifier, coupling agent, oxidation inhibitor and lubricant I;
2) PBT resin, interface modifier and coupling agent are joined to high-speed mixer, mix 30 seconds;
3) add toughner, oxidation inhibitor and lubricant I, continue to mix 60 seconds;
4) raw material mixing is joined in twin screw extruder, special basalt fibre adds by adding fine mouthful, and 220 DEG C～260 DEG C melt extrude, and cooling and dicing obtains matrix material.
10. in the electronic and electric components that the aging basalt fibre enhancing of the high temperature heat-resistant described in claim 1～9 any one polybutylene terephthalate matrix material requires at long term high temperature Working environment and machinofacture parts, apply.
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| CN106749949A (en) * | 2016-12-03 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of modified unsaturated polyester resin of excellent ageing-resistant performance and preparation method thereof |
| CN107298832A (en) * | 2016-11-29 | 2017-10-27 | 德阳力久云智知识产权运营有限公司 | A kind of basalt fibre enhancing polybutylene terephthalate (PBT) composite and preparation method thereof |
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| CN104151791A (en) * | 2014-07-28 | 2014-11-19 | 滁州优胜高分子材料有限公司 | High-temperature-hydrolysis-resistant PBT (polybutylene terephthalate) material |
| CN106283315A (en) * | 2016-09-14 | 2017-01-04 | 四川力久云智知识产权运营有限公司 | A kind of compound basalt fibre carrier material and preparation method thereof |
| CN106283315B (en) * | 2016-09-14 | 2019-05-24 | 四川力久云智知识产权运营有限公司 | A kind of compound basalt fibre carrier material and preparation method thereof |
| CN107298832A (en) * | 2016-11-29 | 2017-10-27 | 德阳力久云智知识产权运营有限公司 | A kind of basalt fibre enhancing polybutylene terephthalate (PBT) composite and preparation method thereof |
| CN106749949A (en) * | 2016-12-03 | 2017-05-31 | 安徽富丽华化工有限公司 | A kind of modified unsaturated polyester resin of excellent ageing-resistant performance and preparation method thereof |
| CN108385392A (en) * | 2018-04-04 | 2018-08-10 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method based on rare-earth element modified heat-resistant textiles |
| CN112143179A (en) * | 2019-06-28 | 2020-12-29 | 合肥杰事杰新材料股份有限公司 | PBT composite material and preparation method thereof |
| CN112143179B (en) * | 2019-06-28 | 2022-04-26 | 合肥杰事杰新材料股份有限公司 | PBT composite material and preparation method thereof |
| CN111454477A (en) * | 2020-04-20 | 2020-07-28 | 李瑞林 | High-temperature-resistant APET (amorphous polyethylene terephthalate) antistatic material and manufacturing method thereof |
| CN113085288A (en) * | 2021-03-06 | 2021-07-09 | 嘉兴学院 | Preparation method of basalt fabric reinforced poly (butylene succinate) composite material plate |
| CN117264387A (en) * | 2023-11-21 | 2023-12-22 | 东莞市国亨塑胶科技有限公司 | Composite polybutylene terephthalate material, preparation method and product thereof |
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Denomination of invention: The invention relates to a basalt fiber reinforced polybutylene terephthalate composite resistant to high temperature thermal aging and a preparation method thereof Effective date of registration: 20211220 Granted publication date: 20160120 Pledgee: Dongyang sub branch of Bank of China Ltd. Pledgor: HENGDIAN GROUP DEBANG ENGINEERING PLASTIC CO.,LTD. Registration number: Y2021330002568 |
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