CN107964211A - A kind of impact modification polyformaldehyde material and preparation method thereof - Google Patents

A kind of impact modification polyformaldehyde material and preparation method thereof Download PDF

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Publication number
CN107964211A
CN107964211A CN201711270649.5A CN201711270649A CN107964211A CN 107964211 A CN107964211 A CN 107964211A CN 201711270649 A CN201711270649 A CN 201711270649A CN 107964211 A CN107964211 A CN 107964211A
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polyformaldehyde
parts
barium sulfate
nano barium
electric field
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舒春柳
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Sichuan Lizhi Jiuchuang Intellectual Property Operations Ltd
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Sichuan Lizhi Jiuchuang Intellectual Property Operations Ltd
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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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of impact modification polyformaldehyde material and preparation method thereof, including following parts by weight raw material to be prepared：60 70 parts of polyformaldehyde, 15 20 parts of nano barium sulfate, 58 parts of modifying agent, 15 25 parts of butadiene rubber, 0.5 0.8 parts of coupling agent, 0.1 0.3 parts of crosslinking agent, 13 parts of zinc stearate；The present invention is for composite by the nano barium sulfate Jing Guo specific aim modification and polyformaldehyde, and nano barium sulfate is dispersed in polyformaldehyde system, and obtained modified polyformaldehyde material excellent shock resistance, is conducive to application of the polyformaldehyde in more areas.

Description

A kind of impact modification polyformaldehyde material and preparation method thereof
Technical field
The present invention relates to modified material field, and in particular to a kind of impact modification polyformaldehyde material and preparation method thereof.
Background technology
Polyformaldehyde is a kind of engineering plastics of function admirable, is the polymer of formaldehyde, is the resin of highly crystalline.With suction Water-based small, dimensional stability, glossiness are good, and heat resistanceheat resistant intensity, bending strength, endurance life are high, wearability and excellent electrical properties Many advantages, such as.Polyformaldehyde is widely used in the field such as electric, mechanical, instrument, daily light industry, automobile, building materials, agricultural. In the application of many frontiers, such as medical technology, sports apparatus etc., polyformaldehyde also shows preferable growing trend.
With the continuous improvement that people require material shock resistance, the polyformaldehyde without impact modification has been difficult to full Sufficient demand, thus, impact modification is carried out to polyformaldehyde and is necessitated.Now to the impact modification processing method kind of polyformaldehyde Class is various, and modified effect is also fine, especially with the appearance and application of nano material, the impact resistance increase effect of polyformaldehyde Significantly, polyformaldehyde is enable largely to be used in more areas, but there is also deficiency.Although nano material has shock resistance enhancing effect It is good, the advantages of additive amount is small, but there is also difficulties in dispersion, it is of high cost the defects of.During impact modification is carried out, nanometer material The scattered inequality of material can influence its shock resistance effect, and obtained modified material impact resistance is relatively low, production to modified material and should With adversely affecting.
The content of the invention
The defects of it is an object of the invention to overcome existing polyformaldehyde material impact resistance poor, there is provided a kind of anti-impact clicks to change Property polyformaldehyde material and preparation method thereof；The present invention is answered the nano barium sulfate Jing Guo specific aim modification and polyformaldehyde Close, and nano barium sulfate is dispersed in polyformaldehyde system, obtained modified polyformaldehyde material excellent shock resistance, has Beneficial to application of the polyformaldehyde in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of impact modification polyformaldehyde material, including it is following heavy Amount part raw material are prepared：60-70 parts of polyformaldehyde, 15-20 parts of nano barium sulfate, 5-8 parts of modifying agent, 15-25 parts Butadiene rubber, 0.5-0.8 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of zinc stearate.
A kind of above-mentioned impact modification polyformaldehyde material, can increase resin material shock resistance according to nano barium sulfate and crosslinking The basic principle of property, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nano barium sulfate Compatibility between polyformaldehyde, and make nano barium sulfate disperse evenly, to make nano barium sulfate to polyformaldehyde in polyformaldehyde Impact resistance humidification it is more preferable, also make modified modified polyformaldehyde material anti-by controlling the degree of polymerization of polyformaldehyde Reach optimum balance relation between impact and processability, so that the modified polyformaldehyde material made is with excellent anti-impact Under conditions of hitting property, it may have excellent processability, allows it to be applied in more areas.
A kind of above-mentioned impact modification polyformaldehyde material, wherein, the nano barium sulfate particle diameter is 10-80nm；Nanometer Barium sulfate particle diameter is smaller, and dispersiveness is poorer, and nano barium sulfate particle diameter is bigger, and the shock resistance humidification to polyformaldehyde is poorer；It is excellent Choosing, the nano barium sulfate particle diameter is 15-25nm；Most preferably, the nano barium sulfate particle diameter is 40nm.
A kind of above-mentioned impact modification polyformaldehyde material, wherein, the modifying agent is ethylene glycol dimethacrylate With the mixture of n-vinyl pyrrolidone composition；The modifying agent can improve the compatible of nano barium sulfate and polyformaldehyde Property, and polar group can be formed on nano barium sulfate surface, beneficial to scattered；Preferably, glycol dinitrate in the modifying agent The ratio between amount of material of base acrylate and n-vinyl pyrrolidone is 1 ︰ 2.
A kind of above-mentioned impact modification polyformaldehyde material, wherein, the degree of polymerization of butadiene rubber is bigger, then is crosslinked post-modification and gathers The impact resistance of formaldehyde materials is poorer, and processability is better, and the polymer of butadiene rubber is smaller, then is crosslinked post-modification polyformaldehyde material Impact resistance it is better, processability is poorer, therefore, selects the rational butadiene rubber degree of polymerization, is balance impact resistance and processing The important means of property.The degree of polymerization of the butadiene rubber is 380-480；Preferably, the degree of polymerization of the butadiene rubber is 400-450；Optimal, the degree of polymerization of the butadiene rubber is 430；By preferred, obtained modified polyformaldehyde material both had There is excellent impact resistance, it may have preferable processability, is adapted to.
Wherein, the polyformaldehyde degree of polymerization is 800-1200；Preferably, the degree of polymerization of the polyformaldehyde is 900- 1100；Most preferably, the degree of polymerization of the polyformaldehyde is 1000；By preferred, obtained modified polyformaldehyde material both had Excellent impact resistance, it may have preferable processability.
A kind of above-mentioned impact modification polyformaldehyde material, wherein, (pyrophosphoric acid two is pungent for isopropyl three for the coupling agent Ester) titanate coupling agent；Isopropyl three (dioctyl pyrophosphate) titanate esters can increase nano barium sulfate and polyformaldehyde and modification Compatibility between agent, improves the shock resistance of modified polyformaldehyde material.
Wherein, the crosslinking agent is polypropylene glycol glycidol ether, which can be by the poly- of two kinds of different polymerization degrees Compound raw material are suitably crosslinked, and improve the impact resistance of modified polyformaldehyde material.
A kind of above-mentioned impact modification polyformaldehyde material, wherein, its raw material further includes dispersant, plasticizer, antistatic One or more auxiliary agents in agent, coloring agent, brightener；Above-mentioned auxiliary agent can improve the processability of modified polyformaldehyde material, increase Its feature etc. is added to act on, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of impact modification polyformaldehyde material Preparation method, comprise the following steps：
（1）Nano barium sulfate is handled with coupling agent；
（2）Nano barium sulfate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano barium sulfate after cladding and polyformaldehyde processing for composite in the electric field after mixing, mixture is obtained；
（4）By mixture and butadiene rubber, crosslinking agent, zinc stearate after mixing in processing for composite, shock resistance is obtained Modified polyformaldehyde material.
A kind of preparation method of impact modification polyformaldehyde material, first carries out at coupling nano barium sulfate with coupling agent Reason, increase nano barium sulfate and modifying agent, the compatibility of polyformaldehyde；Processing is modified to nano barium sulfate with modifying agent again, And form polar group on its surface；Finally make the polar group pole in nano barium sulfate surface and focused beam-forming using external electric field Change, it is powered,, also can be with polyformaldehyde while making nano barium sulfate dispersed by repelling each other between electric charge or attracting principle Polar group on chain is bonded, so that the shock resistance enhancing effect of nano barium sulfate is farthest embodied, so as to get Modified polyacetal impact resistance significantly improve；The preparation method is simple and reliable, is suitable for impact modification polyformaldehyde material Extensive, industrialized production.
A kind of preparation method of above-mentioned impact modification polyformaldehyde material, wherein, it is preferred that step 1 carries out coupling processing During can use ultrasonic wave aid in；Shaken by the high speed of ultrasonic wave, make nano barium sulfate dispersiveness more preferable, and to coupling at Reason has facilitation.
A kind of preparation method of above-mentioned impact modification polyformaldehyde material, wherein, the electric field energy described in step 3 is to group Polarization is produced, makes group powered, so as to promote the scattered and bonded effect of nano barium sulfate, improves modified polyacetal Impact resistance.
Preferably, the electric field strength is 1.5-3.0kv/m；Electric field strength is too small, and polarization effect is weak, to nanometer sulfuric acid The dispersion effect of barium is poor；Electric field strength is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces displacement, Arrangement and the bonded shock resistance for having an impact, may be decreased modified polyformaldehyde material to strand；Most preferably, it is described Electric field strength be 2.0-2.5kv/m.
Wherein, it is preferred that the 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 stablized, to the scattered and bonded facilitation of nano barium sulfate Best results.
Compared with prior art, beneficial effects of the present invention：
1st, impact modification polyformaldehyde material of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes to receive Compatibility between nano-barium sulfate and polyformaldehyde is more preferable, and the dispersiveness in polyformaldehyde is more preferable, and nano barium sulfate is to polyformaldehyde Impact resistance humidification is more preferable.
2nd, impact modification polyformaldehyde material of the present invention makes modification by controlling the degree of polymerization of polyformaldehyde and butadiene rubber Modified polyformaldehyde material afterwards reaches optimum balance relation between impact resistance and processability, so as to get modified polyacetal material Material is under conditions of with excellent impact resistance, it may have excellent processability.
3rd, the preparation method of impact modification polyformaldehyde material of the present invention, using the polarization of external electric field, can promote to receive Nano-barium sulfate is scattered and bonded in polyformaldehyde system, and the shock resistance enhancing effect of nano barium sulfate is more preferable, obtained modification The impact resistance higher of polyformaldehyde material.
4th, preparation method of the present invention is simple, reliable, is adapted to extensive, the industrial metaplasia of impact modification polyformaldehyde material Production.
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）18 parts of nano barium sulfate is handled with 0.5 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）By the nano barium sulfate Jing Guo coupling agent treatment 2 parts of ethylene glycol dimethacrylate and 4 parts of N- vinyl Pyrrolidones carries out cladding processing；
（3）It is in electric field strength after mixing by the polyformaldehyde that the nano barium sulfate after cladding is 1000 with 65 parts of the degree of polymerization Extruded in the constant parallel electric field of the direction of an electric field of 2.5kv/m, obtain mixture；
（4）Butadiene rubber, the 0.2 part of polypropylene glycol glycidol of the mixture that step 3 is obtained and 20 parts of the degree of polymerization for 430 Ether, 2 parts of zinc stearate are extruded after mixing, obtain impact modification polyformaldehyde material.
Embodiment 2
（1）15 parts of nano barium sulfate is handled with 0.3 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）By the nano barium sulfate Jing Guo coupling agent treatment 4 parts of ethylene glycol dimethacrylate and 4 parts of N- vinyl Pyrrolidones carries out cladding processing；
（3）By polyformaldehyde that the nano barium sulfate after cladding and 60 parts of the degree of polymerization are 1200 after mixing in electric field strength To be extruded in the electric field of 1.5kv/m, mixture is obtained；
（4）Butadiene rubber, the 0.3 part of polypropylene glycol glycidol of the mixture that step 3 is obtained and 15 parts of the degree of polymerization for 380 Ether, 3 parts of zinc stearate are extruded after mixing, obtain impact modification polyformaldehyde material.
Embodiment 3
（1）20 parts of nano barium sulfate is handled with 0.8 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）By the nano barium sulfate Jing Guo coupling agent treatment 2 parts of ethylene glycol dimethacrylate and 3 parts of N- vinyl Pyrrolidones carries out cladding processing；
（3）By polyformaldehyde that the nano barium sulfate after cladding and 70 parts of the degree of polymerization are 800 after mixing in electric field strength To be extruded in the constant parallel electric field of the direction of an electric field of 3.0kv/m, mixture is obtained；
（4）Butadiene rubber, the 0.1 part of polypropylene glycol glycidol of the mixture that step 3 is obtained and 25 parts of the degree of polymerization for 480 Ether, 1 part of zinc stearate are extruded after mixing, obtain impact modification polyformaldehyde material.
Comparative example 1
（1）18 parts of nano barium sulfate is handled with 0.5 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment and 5 parts of dispersant, the polyformaldehyde that 65 parts of the degree of polymerization is 1000 are mixed Extruded after closing uniformly in the constant parallel electric field of the direction of an electric field that electric field strength is 2.5kv/m, obtain mixture；
（3）Butadiene rubber, the 0.2 part of polypropylene glycol glycidol of the mixture that step 2 is obtained and 20 parts of the degree of polymerization for 430 Ether, 2 parts of zinc stearate are extruded after mixing, obtain modified polyformaldehyde material.
Comparative example 2
（1）18 parts of nano barium sulfate is handled with 0.5 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）By the nano barium sulfate Jing Guo coupling agent treatment 2 parts of ethylene glycol dimethacrylate and 4 parts of N- vinyl Pyrrolidones carries out cladding processing；
（3）By polyformaldehyde that the nano barium sulfate after cladding is 1000 with 65 parts of the degree of polymerization, 20 parts of the degree of polymerization be 430 it is suitable Buna, 0.2 part of polypropylene glycol glycidol ether, 2 parts of zinc stearate are extruded after mixing, obtain modified polyacetal Material.
Comparative example 3
（1）18 parts of nano barium sulfate is handled with 0.5 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）Nano barium sulfate Jing Guo coupling agent treatment is carried out with 2 parts of polystyrene and 4 parts of n-vinyl pyrrolidone Cladding processing；
（3）It is in electric field strength after mixing by the polyformaldehyde that the nano barium sulfate after cladding is 1000 with 65 parts of the degree of polymerization Extruded in the constant parallel electric field of the direction of an electric field of 2.5kv/m, obtain mixture；
（4）Butadiene rubber, the 0.2 part of polypropylene glycol glycidol of the mixture that step 3 is obtained and 20 parts of the degree of polymerization for 430 Ether, 2 parts of zinc stearate are extruded after mixing, obtain modified polyformaldehyde material.
Comparative example 4
（1）18 parts of nano barium sulfate is handled with 0.5 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）By the nano barium sulfate Jing Guo coupling agent treatment 2 parts of ethylene glycol dimethacrylate and 4 parts of N- vinyl Pyrrolidones carries out cladding processing；
（3）Nano barium sulfate after cladding is shunk with butadiene rubber that 20 parts of the degree of polymerization is 430,0.2 part of polypropylene glycol sweet The polyformaldehyde that oily ether, 2 parts of zinc stearate, 65 parts of the degree of polymerization are 1000 is after mixing 2.5kv/m's in electric field strength Extruded in the constant parallel electric field of direction of an electric field, obtain modified polyformaldehyde material.
Comparative example 5
（1）18 parts of nano barium sulfate is handled with 0.5 part isopropyl three (dioctyl pyrophosphate) titanate esters；
（2）By the nano barium sulfate Jing Guo coupling agent treatment 2 parts of ethylene glycol dimethacrylate and 4 parts of N- vinyl Pyrrolidones carries out cladding processing；
（3）It is in electric field strength after mixing by the polyformaldehyde that the nano barium sulfate after cladding is 700 with 65 parts of the degree of polymerization Extruded in the constant parallel electric field of the direction of an electric field of 2.5kv/m, obtain mixture；
（4）Butadiene rubber that the mixture that step 3 is obtained and 20 parts of the degree of polymerization are 350,0.2 part of zinc stearate, 4 parts it is poly- Propylene glycol glycidyl ether is extruded after mixing, obtains modified polyformaldehyde material.
By the modified polyformaldehyde material in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data are such as Under：
Performance Notch impact strength（KJ/m2） Processability
Embodiment 1 17.2 ++++
Embodiment 2 17.0 ++++
Embodiment 3 17.1 ++++
Comparative example 1 13.8 ++++
Comparative example 2 14.5 ++++
Comparative example 3 15.2 ++++
Comparative example 4 15.6 ++++
Comparative example 5 17.6 ++
Polyformaldehyde 6.2 +++
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the modified polyformaldehyde material of the present invention being prepared in embodiment 1-3, nanometer Barium sulfate is uniformly dispersed, good with the compatibility of polyformaldehyde, modified polyformaldehyde material good impact resistance, and processability is good；And comparative example 1 In, modifying agent is not used processing is modified to nano barium sulfate, although adding dispersant, nano barium sulfate dispersion effect Difference, the poor compatibility with polyformaldehyde, the impact resistance of modified polyformaldehyde material significantly reduce；In comparative example 2 not in the electric field into Row combined processing, nano barium sulfate dispersion effect is poor, and the impact resistance of modified polyformaldehyde material significantly reduces；Change in comparative example 3 Property agent is not the application defined, and nano barium sulfate dispersion effect is poor, and the impact resistance of modified polyformaldehyde material significantly reduces； Cross-linking reaction equally carries out in the electric field in comparative example 4, and electric field has a negative impact cross-linking reaction, so as to get the poly- first of modification The impact resistance of aldehyde material reduces；The polyformaldehyde and the butadiene rubber degree of polymerization used in comparative example 5 is too small, although anti-impact after compound Hitting property increased, but its processability significantly reduces, and be unfavorable for the application of impact modification polyformaldehyde material.

Claims (10)

1. a kind of impact modification polyformaldehyde material, it is characterised in that be prepared including following parts by weight raw material：60-70 The polyformaldehyde of part, 15-20 parts of nano barium sulfate, 5-8 parts of modifying agent, 15-25 parts of butadiene rubber, 0.5-0.8 parts of idol Join agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of zinc stearate；The modifying agent is ethylene glycol dimethacrylate and N- second The mixture of vinyl pyrrolidone composition；The coupling agent is isopropyl three (dioctyl pyrophosphate) titanate coupling agent, described Crosslinking agent is polypropylene glycol glycidol ether；The degree of polymerization of the butadiene rubber is 380-480；The polyformaldehyde degree of polymerization is 800-1200。
2. modified polyformaldehyde material according to claim 1, it is characterised in that ethylene glycol dimethyl third in the modifying agent The ratio between amount of material of olefin(e) acid ester and n-vinyl pyrrolidone is 1 ︰ 2.
3. modified polyformaldehyde material according to claim 1, it is characterised in that the degree of polymerization of the butadiene rubber is 400- 450。
4. modified polyformaldehyde material according to claim 3, it is characterised in that the degree of polymerization of the butadiene rubber is 430.
5. modified polyformaldehyde material according to claim 1, it is characterised in that the polyformaldehyde degree of polymerization is 900- 1100。
6. modified polyformaldehyde material according to claim 5, it is characterised in that the polyformaldehyde degree of polymerization is 1100.
7. a kind of preparation method of the modified polyformaldehyde material as described in claim any one of 1-6, it is characterised in that including following Step：
（1）Nano barium sulfate is handled with coupling agent；
（2）Nano barium sulfate Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano barium sulfate after cladding and polyformaldehyde processing for composite in the electric field after mixing, mixture is obtained； （4）By mixture and butadiene rubber, crosslinking agent, zinc stearate after mixing in processing for composite, impact modification is obtained Polyformaldehyde material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric field strength is 1.5-3.0kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric field strength is 2.0-2.5kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field is put down for direction of an electric field is constant Row electric field.
CN201711270649.5A 2017-12-05 2017-12-05 A kind of impact modification polyformaldehyde material and preparation method thereof Withdrawn CN107964211A (en)

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