CN107298832A - A kind of basalt fibre enhancing polybutylene terephthalate (PBT) composite and preparation method thereof - Google Patents
A kind of basalt fibre enhancing polybutylene terephthalate (PBT) composite and preparation method thereof Download PDFInfo
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- CN107298832A CN107298832A CN201611073621.8A CN201611073621A CN107298832A CN 107298832 A CN107298832 A CN 107298832A CN 201611073621 A CN201611073621 A CN 201611073621A CN 107298832 A CN107298832 A CN 107298832A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The invention discloses a kind of basalt fibre enhancing polybutylene terephthalate (PBT) composite and preparation method thereof, the present invention carries out surface modification treatment first with modifying agent to basalt fibre, the modifying agent includes hypophosphites, highly basic and maleate, increase fiber surface roughness and form a large amount of avtive spots and active group, so as to increase the compatibility of basalt fibre and polybutylene terephthalate (PBT) material, basalt fibre is set to carry out chemical bonding and mechanical riveted with polybutylene terephthalate (PBT) material, the basalt fibre Jing Guo modification and polybutylene terephthalate (PBT) Material cladding are obtained into the more excellent basalt fibre of performance again strengthens polybutylene terephthalate (PBT) composite.
Description
Technical field
The present invention relates to polybutylene terephthalate (PBT) field of compound material, and in particular to a kind of basalt fibre enhancing
Polybutylene terephthalate (PBT) composite and preparation method thereof.
Background technology
Basalt fibre is a kind of emerging novel inorganic environment-friendly and green high performance fibre material, is following China's emphasis
One of four big high-performance fibers of development, it is aoxidized by silica, aluminum oxide, calcium oxide, iron oxide and titanium dioxide etc.
The basalt building stones of thing composition are prepared from after high-temperature fusion by spinning technique.Basalt continuous fiber is not only stablized
Property it is good, but also with a variety of excellent properties such as electrical insulating property, anticorrosive, flame resistant, high temperature resistant, moreover, basalt fibre
The discarded object that production technology is produced is few, and environmental pollution is small, directly can be transferred to after product abandonment in ecological environment, without any danger
Evil, thus be a kind of qualified green, environment-friendly materials.Basalt continuous fiber is in fibre reinforced composites, friction
The many aspects such as material, shipbuilding materials, heat-barrier material, automobile industry, high temperature filtration fabric and protection field have been obtained extensively
Application.
Polybutylene terephthalate (PBT) (abbreviation PBT）Also known as polytetramethylene terephthalate, it is by benzene two
The polyester that formic acid and BDO polycondensation are made.One of most important thermoplastic polyester, five large-engineering plastics, with heat resistance
The advantages of good, good toughness, endurance, self-lubricating, low-friction coefficient；But because ester group is active in polybutylene terephthalate (PBT)
Property it is good, cause polybutylene terephthalate (PBT) material exist intolerant to strong acid, highly basic, flammable, the defect decomposed under high temperature, because
This, many without using pure polybutylene terephthalate (PBT) material when in use, polybutylene terephthalate (PBT) material needs
It could be applied after carrying out the composite modified processing of the enhancing such as fire-retardant, corrosion-resistant, high temperature resistant.Now to poly terephthalic acid fourth two
The fiber-reinforced modified main use glass fiber material of alcohol ester material is modified processing, and modified effect is notable, but glass fibers
Tie up production cost height, environmental pollution greatly, seriously limit glass fibre in polybutylene terephthalate (PBT) material modification
Using therefore, glass being substituted using nontoxic, pollution-free, wide material sources, excellent performance, the basalt fiber material stablized
Fiber strengthens polybutylene terephthalate (PBT) material, and basalt fibre strengthens poly terephthalic acid fourth obtained from
Terephthalate composite is the new direction of polybutylene terephthalate (PBT) composite development.But because basalt fibre is nothing
Machine material, and polybutylene terephthalate (PBT) is macromolecule organic material, both poor compatibilities, and basalt fibre itself knot
Structure and performance are stable, and fiber surface is smooth, surface-active site is few, causes basalt fibre to be more difficult to and gather in modifying process
Mutual-phenenyl two acid bromide two alcohol ester's material carries out chemical bonding and mechanical riveted, i.e., basalt fibre is in polybutylene terephthalate
It is to be individually present in ester material, basalt fibre enhancing poly- pair not good to polybutylene terephthalate (PBT) Material reinforcement effect
The poor-performing of benzene dicarboxylic acid butanediol ester composite.
The content of the invention
It is poor it is an object of the invention to overcome basalt fibre to strengthen polybutylene terephthalate (PBT) composite property
Defect there is provided a kind of basalt fibre enhancing polybutylene terephthalate (PBT) composite and preparation method thereof；The present invention
Surface modification treatment is carried out to basalt fibre first with modifying agent, increases fiber surface roughness and forms a large amount of active sites
Point and active group, so as to increase the compatibility of basalt fibre and polybutylene terephthalate (PBT) material, make basalt fine
Dimension can carry out chemical bonding and machinery riveted with polybutylene terephthalate (PBT) material, then by the basalt Jing Guo modification
Fiber obtains the more excellent basalt fibre enhancing poly terephthalic acid of performance with polybutylene terephthalate (PBT) Material cladding
Butanediol ester composite.
In order to realize foregoing invention purpose, polybutylene terephthalate is strengthened the invention provides a kind of basalt fibre
The preparation method of ester composite, comprises the following steps：
（1）Pretreatment：Basalt fibre is carried out with modifying agent to pre-process to obtain treated basalt fiber；
（2）It is compound：Treated basalt fiber and polybutylene terephthalate (PBT) material are subjected to Combined Processing, basalt is obtained
TR-RFT composite.
A kind of above-mentioned basalt fibre strengthens in the preparation method of polybutylene terephthalate (PBT) composite, step 1
Described modifying agent includes hypophosphites, highly basic and maleate；The modifying agent can to basalt fibre surface corrosion,
Activation, forms rough surface, and is grafted various active group, fiber surface is formed a large amount of avtive spots and active group, from
And chemical bonding and mechanical riveted can be carried out with polybutylene terephthalate (PBT)；Described mechanical riveted refers to that matrix material leads to
Cross the frictional engagement that shrinkage stress packs tightly the fiber of rough surface and produced.
It is preferred that, described modifying agent includes the hypophosphites, the highly basic of 5-10 parts by weight, 10-15 weight of 2-5 parts by weight
Part maleate, the water of 60-100 parts by weight, by preferred, modifying agent is easily-controllable to the modification degree of basalt fibre
System, it is more preferable to basalt fibre modified effect；Most preferably, described modifying agent includes the hypophosphites of 3 parts by weight, 8 weight
The highly basic, the maleate of 12 parts by weight, the water of 80 parts by weight of part.
A kind of above-mentioned basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, wherein described
Hypophosphites be dimethyl hypophosphites, ethylmethylphosphiniacid acid salt, methyl n-propyl hypophosphites, dimethylamino methane base time phosphorus
The one or more of hydrochlorate, benzene-Isosorbide-5-Nitrae-dimethyl hypophosphites, aminomethyl phenyl hypophosphites or diphenyl hypophosphites；It is described
Highly basic one or both of for sodium hydroxide, potassium hydroxide；Described maleate is maleic acid sodium, along fourth
One or both of enedioic acid potassium.
A kind of basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, and the inventive method is first
Basalt fibre is pre-processed using modifying agent, in preprocessing process, modifying agent makes the increase of fiber surface roughness simultaneously
A large amount of avtive spots and active group are formed, basalt fibre is added compatible with polybutylene terephthalate (PBT) material
Property；The basalt fibre by pretreatment and polybutylene terephthalate (PBT) material are combined again, so that basalt
Fiber can carry out chemical bonding and mechanical riveted with polybutylene terephthalate (PBT) material in recombination process, make basalt fine
Dimension forms unified entirety with polybutylene terephthalate (PBT) material, and then obtains the more excellent basalt fibre enhancing of performance
Polybutylene terephthalate (PBT) composite；The inventive method is simple and reliable, and product quality is stable, is adapted to basalt fibre and increases
Extensive, the industrialized production of strong polybutylene terephthalate (PBT) composite.
A kind of above-mentioned basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, wherein step
Basalt fibre described in 1 includes one kind in short basalt fiber, basalt long fiber, continuous basalt fiber.
A kind of above-mentioned basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, wherein step
The temperature pre-processed in 1 is 50-80 DEG C, and temperature is higher, and reaction speed is faster, and control is more difficult, and temperature is lower, and reaction speed is got over
Slowly, reaction effect is poorer；It is preferred that, pretreatment temperature is 55-65 DEG C.
A kind of above-mentioned basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, wherein step
The time pre-processed in 1 is 1-5h, processing time longer, better to basalt fibre surface treatment effect but long processing
Time causes to handle transition, and basalt fiber performance is remarkably decreased, is unfavorable for the enhancing to polybutylene terephthalate (PBT) and changes
Property；It is preferred that, described pretreatment time is 2-3h.
A kind of above-mentioned basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, wherein step
Combined Processing in 2 refers to that will pre-process basalt fibre by process meanses is carried out with polybutylene terephthalate (PBT) material
Chemical bonding and mechanical riveted, make basalt fibre form unified overall side with polybutylene terephthalate (PBT) material
Method.
A kind of above-mentioned basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, wherein step
Treated basalt fiber consumption is the 1-40% of polybutylene terephthalate (PBT) material in 2, and the consumption of treated basalt fiber can
Strengthen polybutylene terephthalate (PBT) composite according to basalt fibre to require to be adjusted in different application field.
A kind of above-mentioned basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, wherein step
2 during Combined Processing is carried out, can also add auxiliary agent, and the auxiliary agent includes dispersant, coupling agent, antiseptic, antistatic
One or more in agent, fire retardant.
It is further, poly- to benzene two the invention provides a kind of enhancing of basalt fibre in order to realize foregoing invention purpose
Formic acid butanediol ester composite, the basalt fibre enhancing polybutylene terephthalate (PBT) composite is by above-mentioned
What preparation method was prepared；The basalt fibre strengthens polybutylene terephthalate (PBT) composite due to basalt fibre
Compatibility with polybutylene terephthalate (PBT) material is good, thus its mechanical performance and physical and chemical performance are more excellent, it is adaptable to more
Multiple environmental conditions, application is wider.
Compared with prior art, beneficial effects of the present invention：
1st, the inventive method is modified processing to basalt fibre using modifying agent, makes the increase of fiber surface roughness, so that
It is that basalt fibre can carry out mechanical riveted with polybutylene terephthalate (PBT) material, the basalt fibre enhancing prepared
The mechanical performance of polybutylene terephthalate (PBT) composite is more preferable.
2nd, the inventive method is pre-processed using modifying agent to basalt fibre, enables basalt fibre with poly- to benzene two
Formic acid butanediol ester material is chemically bonded in recombination process, the basalt fibre enhancing poly terephthalic acid prepared
The physical and chemical performance of butanediol ester composite is more preferable.
3rd, basalt fibre enhancing polybutylene terephthalate (PBT) composite of the present invention, because basalt fibre is with gathering
The compatibility of mutual-phenenyl two acid bromide two alcohol ester's material is good, thus its mechanical performance and physical and chemical performance are more excellent, it is adaptable to more
Environmental condition, application is wider.
Embodiment
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of above-mentioned theme of the invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）Pretreatment：By dimethyl sodium hypophosphite, the potassium hydroxide of 8 parts by weight, 12 weights of the basalt fibre by 3 parts by weight
Measure in the maleic acid sodium of part, the modifying agent that the water of 80 parts by weight is constituted, pretreatment 2h is carried out at a temperature of 55 DEG C to be changed
Property basalt fibre；
（2）It is compound：The polybutylene terephthalate (PBT) of the treated basalt fiber of 3 parts by weight and 10 parts by weight is combined
Processing, obtains basalt fibre enhancing polybutylene terephthalate (PBT) composite.
Embodiment 2
（1）Pretreatment：By benzene-Isosorbide-5-Nitrae-dimethyl potassium hypophosphite, the hydroxide of 10 parts by weight of the basalt fibre by 2 parts by weight
In sodium, the maleic acid potassium of 15 parts by weight, the modifying agent of the water composition of 100 parts by weight, located in advance at a temperature of 65 DEG C
Reason 3h obtains treated basalt fiber；
（2）It is compound：The polybutylene terephthalate (PBT) of the treated basalt fiber of 3 parts by weight and 10 parts by weight is combined
Processing, obtains basalt fibre enhancing polybutylene terephthalate (PBT) composite.
Embodiment 3
（1）Pretreatment：By basalt fibre with by the ethylmethylphosphiniacid acid sodium of 5 parts by weight, the sodium hydroxide of 5 parts by weight, 10
In the maleic acid potassium of parts by weight, the modifying agent of the water composition of 100 parts by weight, pretreatment 1h is carried out at a temperature of 80 DEG C and is obtained
Treated basalt fiber；
（2）It is compound：The polybutylene terephthalate (PBT) of the treated basalt fiber of 3 parts by weight and 10 parts by weight is combined
Processing, obtains basalt fibre enhancing polybutylene terephthalate (PBT) composite.
Embodiment 4
（1）Pretreatment：By basalt fibre with by the aminomethyl phenyl sodium hypophosphite of 5 parts by weight, the potassium hydroxide of 10 parts by weight, 10
In the maleic acid potassium of parts by weight, the modifying agent of the water composition of 60 parts by weight, pretreatment 5h is carried out at a temperature of 50 DEG C and is obtained
Treated basalt fiber；
（2）It is compound：The polybutylene terephthalate (PBT) of the treated basalt fiber of 3 parts by weight and 10 parts by weight is combined
Processing, obtains basalt fibre enhancing polybutylene terephthalate (PBT) composite.
Comparative example 1
It is compound：The basalt fibre of 3 parts by weight and the polybutylene terephthalate (PBT) of 10 parts by weight are subjected to Combined Processing, obtained
Strengthen polybutylene terephthalate (PBT) composite to basalt fibre.
Comparative example 2
（1）Pretreatment：By dimethyl sodium hypophosphite of the basalt fibre by 3 parts by weight, the maleic acid sodium of 12 parts by weight,
In the modifying agent of the water composition of 80 parts by weight, pretreatment 2h is carried out at a temperature of 55 DEG C and obtains treated basalt fiber；
（2）It is compound：The polybutylene terephthalate (PBT) of the treated basalt fiber of 3 parts by weight and 10 parts by weight is combined
Processing, obtains basalt fibre enhancing polybutylene terephthalate (PBT) composite.
Comparative example 3
（1）Pretreatment：By potassium hydroxide of the basalt fibre by 8 parts by weight, the maleic acid sodium of 12 parts by weight, 80 weight
In the modifying agent of the water composition of part, pretreatment 2h is carried out at a temperature of 55 DEG C and obtains treated basalt fiber；
（2）It is compound：The polybutylene terephthalate (PBT) of the treated basalt fiber of 3 parts by weight and 10 parts by weight is combined
Processing, obtains basalt fibre enhancing polybutylene terephthalate (PBT) composite.
By preparation-obtained basalt fibre enhancing poly terephthalic acid fourth in above-described embodiment 1-4 and comparative example 1-3
Terephthalate composite carries out performance test experiments record experimental result, and record data is as follows：（Polybutylene terephthalate (PBT)
Composite tensile strength 78MPa, notch impact strength 60J/m, 58 DEG C of heat distortion temperature）
| Numbering | Modified polybutylene terephthalate (PBT) plastics breach Impact strength（J/m） | Modified polybutylene terephthalate (PBT) plastics are drawn Stretch intensity（Mpa） | Modified polybutylene terephthalate (PBT) plastics thermal change Shape temperature（℃） |
| Embodiment 1 | 123 | 151 | 246 |
| Embodiment 2 | 120 | 148 | 245 |
| Embodiment 3 | 119 | 150 | 245 |
| Embodiment 4 | 123 | 147 | 246 |
| Comparative example 1 | 94 | 106 | 224 |
| Comparative example 2 | 86 | 116 | 228 |
| Comparative example 3 | 85 | 109 | 233 |
Above-mentioned analysis of experimental data is understood, the basalt fibre prepared in embodiment 1-4 using technical solution of the present invention
Notch impact strength, tensile strength, the heat distortion temperature of enhancing polybutylene terephthalate (PBT) composite, which have, significantly to be carried
Rise；And be directly combined basalt fibre and polybutylene terephthalate (PBT) material in the preparation method of comparative example 1, obtain
Basalt fibre enhancing polybutylene terephthalate (PBT) composite, but because basalt fibre is not modified processing,
Fiber surface activity point position is few and active group is few, poor with polybutylene terephthalate (PBT) material compatibility, with poly- to benzene two
The chemical bonding of formic acid butanediol ester material and mechanical riveted effect are poor, basalt fibre enhancing polybutylene terephthalate (PBT)
Composite property is significantly reduced；The modifying agent used in the preparation method of comparative example 2 is not added with highly basic, it is impossible to basalt fibre
Surface is eroded, and fiber surface can not be activated and is grafted, and basalt fibre surface-active point position is less and active group
Group is few, poor with the chemical bonding of polybutylene terephthalate (PBT) material and mechanical riveted effect, poly- pair of basalt fibre enhancing
Benzene dicarboxylic acid butanediol ester composite property is significantly reduced；The modifying agent used in the preparation method of comparative example 3 is not added with diformazan
Base sodium hypophosphite, it is impossible to carry out grafting and the bonded active group of polybutylene terephthalate (PBT), basalt in fiber surface
Fiber surface activity point position is few and active group is few, and the chemical bonding effect with polybutylene terephthalate (PBT) material is poor, profound
Military rock TR-RFT composite property is significantly reduced.
Claims (10)
1. a kind of basalt fibre strengthens the preparation method of polybutylene terephthalate (PBT) composite, it is characterised in that bag
Include following steps：
（1）Pretreatment：Basalt fibre is carried out with modifying agent to pre-process to obtain treated basalt fiber；
（2）It is compound：Treated basalt fiber and polybutylene terephthalate (PBT) material are subjected to Combined Processing, basalt is obtained
TR-RFT composite；The modifying agent includes hypophosphites, highly basic and maleic acid
Salt.
2. preparation method according to claim 1, it is characterised in that described modifying agent includes the secondary phosphorus of 2-5 parts by weight
Hydrochlorate, the highly basic of 5-10 parts by weight, the maleate of 10-15 parts by weight, the water of 60-100 parts by weight.
3. preparation method according to claim 2, it is characterised in that described modifying agent includes the hypophosphorous acid of 3 parts by weight
Salt, the highly basic of 8 parts by weight, the maleate of 12 parts by weight, the water of 80 parts by weight.
4. the preparation method according to claim any one of 1-3, it is characterised in that the hypophosphites is dimethyl time phosphorus
Hydrochlorate, ethylmethylphosphiniacid acid salt, methyl n-propyl hypophosphites, dimethylamino methane base hypophosphites, benzene-Isosorbide-5-Nitrae-dimethyl time phosphorus
The one or more of hydrochlorate, aminomethyl phenyl hypophosphites or diphenyl hypophosphites.
5. the preparation method according to claim any one of 1-3, it is characterised in that the highly basic is sodium hydroxide, hydrogen-oxygen
Change one or both of potassium.
6. the preparation method according to claim any one of 1-3, it is characterised in that the maleate is maleic
One or both of diacid sodium, maleic acid potassium.
7. preparation method according to claim 1, it is characterised in that the temperature pre-processed in step 1 is 50-80 DEG C.
8. preparation method according to claim 1, it is characterised in that the time pre-processed in step 1 is 1-5h.
9. preparation method according to claim 1, it is characterised in that treated basalt fiber consumption is poly- pair in step 2
The 1-40% of benzene dicarboxylic acid butanediol ester material.
10. a kind of basalt fibre strengthens polybutylene terephthalate (PBT) composite, it is characterised in that being will by right
Ask what the preparation method described in any one of 1-9 was prepared.
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| CN113085288A (en) * | 2021-03-06 | 2021-07-09 | 嘉兴学院 | Preparation method of basalt fabric reinforced poly (butylene succinate) composite material plate |
| EP3919569A1 (en) * | 2020-06-01 | 2021-12-08 | SHPP Global Technologies B.V. | Thermoplastic compositions including natural fiber having good mechanical properties and good dielectric properties |
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| 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 |
| EP3919569A1 (en) * | 2020-06-01 | 2021-12-08 | SHPP Global Technologies B.V. | Thermoplastic compositions including natural fiber having good mechanical properties and good dielectric properties |
| WO2021245500A1 (en) * | 2020-06-01 | 2021-12-09 | Shpp Global Technologies B.V. | Thermoplastic compositions including natural fiber having good mechanical properties and good dielectric properties |
| KR20230006653A (en) * | 2020-06-01 | 2023-01-10 | 에스에이치피피 글로벌 테크놀러지스 비.브이. | Thermoplastic composition comprising natural fibers with good mechanical properties and good dielectric properties |
| KR102589600B1 (en) | 2020-06-01 | 2023-10-16 | 에스에이치피피 글로벌 테크놀러지스 비.브이. | Thermoplastic composition comprising natural fibers with good mechanical properties and good dielectric properties |
| CN113085288A (en) * | 2021-03-06 | 2021-07-09 | 嘉兴学院 | Preparation method of basalt fabric reinforced poly (butylene succinate) composite material plate |
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Application publication date: 20171027 |