CN107815052A - A kind of composite material of polymethyl methacrylate and preparation method thereof - Google Patents
A kind of composite material of polymethyl methacrylate and preparation method thereof Download PDFInfo
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- CN107815052A CN107815052A CN201711270598.6A CN201711270598A CN107815052A CN 107815052 A CN107815052 A CN 107815052A CN 201711270598 A CN201711270598 A CN 201711270598A CN 107815052 A CN107815052 A CN 107815052A
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of composite material of polymethyl methacrylate and preparation method thereof, including following parts by weight raw material to be prepared：50 60 parts of polymethyl methacrylate, 10 15 parts of nano-bentonite, 35 parts of modifying agent, 15 25 parts of Kynoar, 35 parts of coupling agent, 0.3 0.6 parts of crosslinking agent, 10 15 parts of poly-isocyanurate；The present invention carries out the nano-bentonite Jing Guo specific aim modification with polymethyl methacrylate compound, and nano-bentonite is set to be dispersed in polymethyl methacrylate system, obtained composite creep-resistant property is excellent, is advantageous to application of the polymethyl methacrylate in more areas.
Description
Technical field
The present invention relates to material modified field, and in particular to a kind of composite material of polymethyl methacrylate and its preparation side
Method.
Background technology
Polymethyl methacrylate is the polymer being polymerized using methyl methacrylate as monomer, is a kind of thermoplasticity
Plastics.Due to resistance to ag(e)ing is good, translucency is good, good insulating, high mechanical strength, good weatherability, good flame resistance etc. are excellent
Combination property, so obtained for a long time in fields such as electronics, electrical equipment, machinery, automobile, medical apparatus, food processings widely should
With.
With the continuous improvement that people are required material creep-resistant property, the poly-methyl methacrylate being modified without creep resistant
Ester has been difficult to meet demand, thus, creep resistant modification is carried out to polymethyl methacrylate and is necessitated.Now to poly- methyl-prop
The creep resistant modification processing method species of e pioic acid methyl ester is various, and modified effect is also fine, especially with the appearance of nano material
And application, the creep resistance increase significant effect of polymethyl methacrylate, enable polymethyl methacrylate in more areas
It is a large amount of to use, but there is also deficiency.Although nano material has the advantages of creep resistant enhancing effect is good, and addition is small, also deposit
In difficulties in dispersion, the defects of cost is high.In creep resistant modifying process is carried out, nano material, which disperses inequality, can influence its creep resistant
Effect, obtained composite creep resistance is relatively low, and the production and application to composite adversely affect.
The content of the invention
The defects of it is an object of the invention to overcome existing composite material of polymethyl methacrylate creep resistance poor, carry
For a kind of composite material of polymethyl methacrylate and preparation method thereof；The present invention is swollen by the nanometer Jing Guo specific aim modification
Profit soil and polymethyl methacrylate progress are compound, and nano-bentonite is dispersed in polymethyl methacrylate system
In, obtained composite creep-resistant property is excellent, is advantageous to application of the polymethyl methacrylate in more areas.
In order to realize foregoing invention purpose, the invention provides a kind of composite material of polymethyl methacrylate, including with
Lower parts by weight raw material are prepared：The polymethyl methacrylate of 50-60 parts, the nano-bentonite of 10-15 parts, 3-5 parts
Modifying agent, the Kynoar of 15-25 parts, the coupling agent of 3-5 parts, the crosslinking agent of 0.3-0.6 parts, the poly- isocyanide urea of 10-15 parts
Acid esters.
A kind of above-mentioned composite material of polymethyl methacrylate, it can increase resin material according to nano-bentonite and crosslinking and resist
The general principle of creep properties, it is swollen to improve nanometer not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent
Compatibility between profit soil and polymethyl methacrylate, and it is more equal nano-bentonite is disperseed in polymethyl methacrylate
It is even, make creep resistance humidification of the nano-bentonite to polymethyl methacrylate more preferable, also by controlling polymethyl
The degree of polymerization of sour methyl esters makes the modified composite reach optimum balance relation between creep resistance and processability, so as to
The composite for making to obtain is under conditions of with excellent creep resistance, it may have excellent processability, allows it more
It is applied in multi-field.
A kind of above-mentioned composite material of polymethyl methacrylate, wherein, described nano-bentonite particle diameter is 10-80nm；
Nano-bentonite particle diameter is smaller, and dispersiveness is poorer, and nano-bentonite particle diameter is bigger, and the creep resistant of polymethyl methacrylate is increased
It is poorer to pretend use；Preferably, described nano-bentonite particle diameter is 30-50nm；Most preferably, described nano-bentonite particle diameter
For 40nm.
A kind of above-mentioned composite material of polymethyl methacrylate, wherein, described modifying agent is dibutyl tin laurate
With the mixture of aluminum stearate composition；Described modifying agent can improve the compatible of nano-bentonite and polymethyl methacrylate
Property, and can forms polar group on nano-bentonite surface, beneficial to scattered；Preferably, tin dilaurate two in described modifying agent
The ratio between butyl tin and the amount of material of aluminum stearate are 1 ︰ 1.
A kind of above-mentioned composite material of polymethyl methacrylate, wherein, the degree of polymerization of Kynoar is bigger, then after being crosslinked
The creep resistance of composite is poorer, and processability is better, and the polymer of Kynoar is smaller, then composite is anti-after being crosslinked
Creep properties is better, and processability is poorer, therefore, selects the rational Kynoar degree of polymerization, is balance creep resistance and processability
Important means.The degree of polymerization of described Kynoar is 120-200；Preferably, the degree of polymerization of described Kynoar
For 140-180；Optimal, the degree of polymerization of described Kynoar is 160；By preferred, obtained composite both had
Excellent creep resistance, it may have preferable processability, be adapted to the application in more areas.
Wherein, the described polymethyl methacrylate degree of polymerization is 600-1000；Preferably, the poly-methyl methacrylate
The degree of polymerization of ester is 700-900；Most preferably, the degree of polymerization of described polymethyl methacrylate is 800；By preferred, obtain
The composite arrived both has excellent creep resistance, it may have preferable processability.
A kind of above-mentioned composite material of polymethyl methacrylate, wherein, described coupling agent is coupled for the isopropyl ester of aluminic acid three
Agent；The isopropyl ester of aluminic acid three can increase the compatibility between nano-bentonite and polymethyl methacrylate and modifying agent, improve
The performance of composite.
Wherein, described crosslinking agent is paratoluensulfonyl chloride, and the crosslinking agent can be former by the polymer of two kinds of different polymerization degrees
Material is suitably crosslinked, and improves the creep resistance of composite.
A kind of above-mentioned composite material of polymethyl methacrylate, wherein, its raw material also includes dispersant, plasticizer, resisted
One or more auxiliary agents in electrostatic agent, coloring agent, brightener；Above-mentioned auxiliary agent can improve the processability of composite, increase
Its feature etc. acts on, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of polymethyl methacrylate is compound
The preparation method of material, comprises the following steps：
（1）Nano-bentonite is handled with coupling agent；
（2）Nano-bentonite Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nano-bentonite after cladding is well mixed with polymethyl methacrylate in the electric field,
Obtain compound；
（4）Combined Processing is being carried out after compound is well mixed with Kynoar, crosslinking agent, poly-isocyanurate, is being obtained
Polymethyl methacrylate creep-resistant composite material.
A kind of preparation method of composite material of polymethyl methacrylate, is first coupled with coupling agent to nano-bentonite
Processing, increase nano-bentonite and modifying agent, the compatibility of polymethyl methacrylate；Nano-bentonite is entered with modifying agent again
Row modification, and form polar group on its surface；Finally make nano-bentonite surface and polymethyl using external electric field
Polar group polarization in sour methyl esters chain, it is powered, by repelling each other between electric charge or attracting principle, nano-bentonite is uniformly divided
, also can be bonded with the polar group on polymethyl methacrylate chain while dissipating, so that the creep resistant of nano-bentonite increases
Potent fruit is farthest embodied, so as to get modified poly (methyl methacrylate) creep resistance significantly improve；The preparation
Method is simple and reliable, is suitable for extensive, the industrialized production of polymethyl methacrylate creep-resistant composite material.
A kind of preparation method of above-mentioned composite material of polymethyl methacrylate, wherein, it is preferred that step 1 is coupled
Ultrasonic assistant can be used in processing procedure；Shaken by the high speed of ultrasonic wave, make nano-bentonite dispersiveness more preferable, and antithesis
Connection processing has facilitation.
A kind of preparation method of above-mentioned composite material of polymethyl methacrylate, wherein, the electric field energy pair described in step 3
Group produces polarization, makes group powered, so as to promote the scattered and bonded effect of nano-bentonite, improves modified poly- first
The creep resistance of base methyl acrylate.
Preferably, described electric-field intensity is 1.5-2.5kv/m；Electric-field intensity is too small, and polarization effect is weak, to nanometer swelling
The dispersion effect of soil is poor；Electric-field intensity is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces displacement,
Arrangement and the bonded performance for having an impact, composite may being reduced to strand；Most preferably, described electric-field intensity is
1.8-2.0kv/m。
Wherein, it is preferred that described electric field is the constant parallel electric field of direction of an electric field；The constant parallel electric field of direction of an electric field
Best to the polarization effect of polar group, group intermolecular forces are stable, to the scattered and bonded facilitation of nano-bentonite
Best results.
Compared with prior art, beneficial effects of the present invention：
1st, composite of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes nano-bentonite with gathering
Compatibility between methyl methacrylate is more preferable, and the dispersiveness in polymethyl methacrylate is more preferable, nano-bentonite pair
The creep resistance humidification of polymethyl methacrylate is more preferable.
2nd, composite of the present invention makes modification by controlling the degree of polymerization of polymethyl methacrylate and Kynoar
Composite afterwards reaches optimum balance relation between creep resistance and processability, so as to get composite with excellent
Creep resistance under conditions of, it may have excellent processability.
3rd, the preparation method of composite of the present invention, using the polarization of external electric field, nano-bentonite can be promoted poly-
Scattered and bonded in methyl methacrylate system, the creep resistant enhancing effect of nano-bentonite is more preferable, obtained composite wood
The creep resistance of material is higher.
4th, the preparation method of composite of the present invention is simple, reliable, is adapted to polymethyl methacrylate creep resistant composite wood
Extensive, the industrialized production of material.
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 the above-mentioned theme of the present 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）12 parts of nano-bentonite is handled with 4 parts of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is carried out with 2 parts of dibutyl tin laurate and 2 parts of aluminum stearate
Cladding processing；
（3）After nano-bentonite after cladding is well mixed with the polymethyl methacrylate that 55 parts of the degree of polymerization is 800
Electric-field intensity is to be extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtains compound；
（4）Kynoar that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 160,0.5 part of paratoluensulfonyl chloride,
Extruded after 12 parts of poly-isocyanurate is well mixed, obtain polymethyl methacrylate creep-resistant composite material.
Embodiment 2
（1）10 parts of nano-bentonite is handled with 3 parts of the isopropyl ester of aluminic acid three；
（2）By the nano-bentonite Jing Guo coupling agent treatment 1.5 parts of dibutyl tin laurate and 1.5 parts of aluminum stearate
Carry out cladding processing；
（3）After nano-bentonite after cladding is well mixed with the polymethyl methacrylate that 50 parts of the degree of polymerization is 600
Extruded in the electric field that electric-field intensity is 1.5kv/m, obtain compound；
（4）Kynoar that the compound that step 3 is obtained and 15 parts of the degree of polymerization are 120,0.3 part of paratoluensulfonyl chloride,
Extruded after 10 parts of poly-isocyanurate is well mixed, obtain polymethyl methacrylate creep-resistant composite material.
Embodiment 3
（1）15 parts of nano-bentonite is handled with 5 parts of the isopropyl ester of aluminic acid three；
（2）By the nano-bentonite Jing Guo coupling agent treatment 2.5 parts of dibutyl tin laurate and 2.5 parts of aluminum stearate
Carry out cladding processing；
（3）After nano-bentonite after cladding is well mixed with the polymethyl methacrylate that 60 parts of the degree of polymerization is 1000
Extruded in the constant parallel electric field of the direction of an electric field that electric-field intensity is 2.5kv/m, obtain compound；
（4）Kynoar that the compound that step 3 is obtained and 25 parts of the degree of polymerization are 200,0.6 part of paratoluensulfonyl chloride,
Extruded after 15 parts of poly-isocyanurate is well mixed, obtain polymethyl methacrylate creep-resistant composite material.
Comparative example 1
（1）12 parts of nano-bentonite is handled with 4 parts of the isopropyl ester of aluminic acid three；
（2）By the nano-bentonite Jing Guo coupling agent treatment and 5 parts of dispersant, the poly- methyl-prop that 55 parts of the degree of polymerization is 900
Extruded, obtained in the constant parallel electric field of the direction of an electric field that electric-field intensity is 2.0kv/m after e pioic acid methyl ester is well mixed
Compound；
（3）Kynoar that the compound that step 2 is obtained and 20 parts of the degree of polymerization are 160,0.5 part of paratoluensulfonyl chloride,
Extruded after 12 parts of poly-isocyanurate is well mixed, obtain composite.
Comparative example 2
（1）12 parts of nano-bentonite is handled with 4 parts of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is carried out with 2 parts of dibutyl tin laurate and 2 parts of aluminum stearate
Cladding processing；
（3）By the polymethyl methacrylate of the nano-bentonite after cladding and 55 parts of the degree of polymerization for 900,20 parts of the degree of polymerization
Extruded, obtained after being well mixed for 160 Kynoar, 0.5 part of paratoluensulfonyl chloride, 12 parts of poly-isocyanurate
Composite.
Comparative example 3
（1）12 parts of nano-bentonite is handled with 4 parts of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is carried out at cladding with 2 parts of Kynoar and 2 parts of aluminum stearate
Reason；
（3）After nano-bentonite after cladding is well mixed with the polymethyl methacrylate that 55 parts of the degree of polymerization is 900
Electric-field intensity is to be extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtains compound；
（4）Kynoar that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 160,0.5 part of paratoluensulfonyl chloride,
Extruded after 12 parts of poly-isocyanurate is well mixed, obtain composite.
Comparative example 4
（1）12 parts of nano-bentonite is handled with 4 parts of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is carried out with 2 parts of dibutyl tin laurate and 2 parts of aluminum stearate
Cladding processing；
（3）By Kynoar that the nano-bentonite after cladding and 20 parts of the degree of polymerization are 160,0.5 part of paratoluensulfonyl chloride,
It is in electric-field intensity after polymethyl methacrylate that 12 parts of poly-isocyanurate, 55 parts of the degree of polymerization are 900 is well mixed
Extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtain composite.
Comparative example 5
（1）12 parts of nano-bentonite is handled with 4 parts of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is carried out with 2 parts of dibutyl tin laurate and 2 parts of aluminum stearate
Cladding processing；
（3）After nano-bentonite after cladding is well mixed with the polymethyl methacrylate that 55 parts of the degree of polymerization is 500
Electric-field intensity is to be extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtains compound；
（4）Kynoar that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 100,12 parts of poly-isocyanurate,
Extruded after 0.5 part of paratoluensulfonyl chloride is well mixed, obtain composite.
By the composite in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data is as follows：
| Performance | Creep resistance | Processability |
| Embodiment 1 | ++++++ | ++++ |
| Embodiment 2 | ++++++ | ++++ |
| Embodiment 3 | ++++++ | ++++ |
| Comparative example 1 | ++++ | ++++ |
| Comparative example 2 | ++++ | ++++ |
| Comparative example 3 | +++++ | ++++ |
| Comparative example 4 | +++++ | ++++ |
| Comparative example 5 | +++++ | ++ |
Note："+" is more, illustrates that performance is better.
The polymethyl methacrylate of the present invention being prepared in embodiment 1-3, which resists, to be understood to above-mentioned analysis of experimental data
Creep composite, nano-bentonite are uniformly dispersed, good with the compatibility of polymethyl methacrylate, composite creep resistance
Good, processability is good；And in comparative example 1, modifying agent is not used processing is modified to nano-bentonite, although adding scattered
Agent, but nano-bentonite dispersion effect is poor, the poor compatibility with polymethyl methacrylate, and the creep resistance of composite is notable
Reduce；Do not carry out Combined Processing in comparative example 2 in the electric field, nano-bentonite dispersion effect is poor, the creep resistance of composite
Significantly reduce；Modifying agent is not the application defined in comparative example 3, and nano-bentonite dispersion effect is poor, and composite resists
Creep properties significantly reduces；Cross-linking reaction is equally carried out in the electric field in comparative example 4, and electric field has a negative impact to cross-linking reaction,
The creep resistance for the composite for making to obtain reduces；The polymethyl methacrylate and Kynoar used in comparative example 5 gathers
Right too small, although creep resistance increased after compound, its processability significantly reduces, and is unfavorable for the application of composite.
Claims (10)
1. a kind of composite material of polymethyl methacrylate, it is characterised in that be prepared including following parts by weight raw material：
The polymethyl methacrylate of 50-60 parts, the nano-bentonite of 10-15 parts, the modifying agent of 3-5 parts, the polyvinylidene fluoride of 15-25 parts
Alkene, the coupling agent of 3-5 parts, the crosslinking agent of 0.3-0.6 parts, the poly-isocyanurate of 10-15 parts；The modifying agent is tin dilaurate
The mixture of dibutyl tin and aluminum stearate composition；The coupling agent is the isopropyl ester coupling agent of aluminic acid three, and the crosslinking agent is pair
Toluene sulfochloride；The degree of polymerization of the Kynoar is 120-200；The polymethyl methacrylate degree of polymerization is 600-
1000。
2. composite according to claim 1, it is characterised in that in the modifying agent dibutyl tin laurate with it is hard
The ratio between amount of material of resin acid aluminium is 1 ︰ 1.
3. composite according to claim 1, it is characterised in that the degree of polymerization of the Kynoar is 140-180.
4. composite according to claim 3, it is characterised in that the degree of polymerization of the Kynoar is 160.
5. composite according to claim 1, it is characterised in that the polymethyl methacrylate degree of polymerization is 700-
900。
6. composite according to claim 5, it is characterised in that the polymethyl methacrylate degree of polymerization is 800.
7. a kind of preparation method of the composite as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nano-bentonite is handled with coupling agent；
（2）Nano-bentonite Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nano-bentonite after cladding is well mixed with polymethyl methacrylate in the electric field,
Obtain compound；
（4）By compound and Kynoar, crosslinking agent, poly-isocyanurate, be well mixed after carrying out Combined Processing, obtain
Polymethyl methacrylate creep-resistant composite material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric-field intensity is 1.5-2.5kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric-field intensity is 1.8-2.0kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field, which is that direction of an electric field is constant, puts down
Row electric field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711270598.6A CN107815052A (en) | 2017-12-05 | 2017-12-05 | A kind of composite material of polymethyl methacrylate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711270598.6A CN107815052A (en) | 2017-12-05 | 2017-12-05 | A kind of composite material of polymethyl methacrylate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107815052A true CN107815052A (en) | 2018-03-20 |
Family
ID=61606772
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| Application Number | Title | Priority Date | Filing Date |
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| CN201711270598.6A Withdrawn CN107815052A (en) | 2017-12-05 | 2017-12-05 | A kind of composite material of polymethyl methacrylate and preparation method thereof |
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| CN (1) | CN107815052A (en) |
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- 2017-12-05 CN CN201711270598.6A patent/CN107815052A/en not_active Withdrawn
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Application publication date: 20180320 |