CN107759968A - A kind of polyformaldehyde creep resistant is material modified and preparation method thereof - Google Patents
A kind of polyformaldehyde creep resistant is material modified and preparation method thereof Download PDFInfo
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- CN107759968A CN107759968A CN201711270650.8A CN201711270650A CN107759968A CN 107759968 A CN107759968 A CN 107759968A CN 201711270650 A CN201711270650 A CN 201711270650A CN 107759968 A CN107759968 A CN 107759968A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
It is material modified and preparation method thereof the invention discloses a kind of polyformaldehyde creep resistant, including following parts by weight raw material are prepared：50 60 parts of polyformaldehyde, 10 15 parts of nano-bentonite, 35 parts of modifying agent, 15 25 parts of nitrile rubber, 0.3 0.6 parts of coupling agent, 35 parts of crosslinking agent, 10 15 parts of polyacrylamide；The present invention is compound by the nano-bentonite Jing Guo specific aim modification and polyformaldehyde progress, and nano-bentonite is dispersed in polyformaldehyde system, and obtained material modified creep-resistant property is excellent, is advantageous to application of the polyformaldehyde in more areas.
Description
Technical field
The present invention relates to modified polyformaldehyde material field, and in particular to a kind of polyformaldehyde creep resistant is material modified and its prepares
Method.
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 are required material creep-resistant property, the polyformaldehyde being modified without creep resistant has been difficult to full
Sufficient demand, thus, creep resistant modification is carried out to polyformaldehyde and is necessitated.Now to the creep resistant 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 creep 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 creep resistant enhancing effect
It is good, the advantages of addition is small, but there is also difficulties in dispersion, the defects of cost is high.In creep resistant modifying process is carried out, nanometer material
The scattered inequality of material can influence its creep resistant effect, and obtained material modified creep resistance is relatively low, to material modified production and answer
With adversely affecting.
The content of the invention
A kind of the defects of it is an object of the invention to overcome existing polyoxymethylene modified material creep resistance poor, there is provided poly- first
Aldehyde creep resistant is material modified and preparation method thereof；The present invention enters the nano-bentonite Jing Guo specific aim modification with polyformaldehyde
Row is compound, and nano-bentonite is dispersed in polyformaldehyde system, and obtained material modified creep-resistant property is excellent, favorably
In application of the polyformaldehyde in more areas.
In order to realize foregoing invention purpose, the invention provides a kind of polyformaldehyde creep resistant is material modified, including it is following heavy
Amount part raw material are prepared：The polyformaldehyde of 50-60 parts, the nano-bentonite of 10-15 parts, the modifying agent of 3-5 parts, 15-25 parts
Nitrile rubber, the coupling agent of 0.3-0.6 parts, the crosslinking agent of 3-5 parts, the polyacrylamide of 10-15 parts.
A kind of above-mentioned polyformaldehyde creep resistant is material modified, can increase resin material creep resistant according to nano-bentonite and crosslinking
The general principle of property, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nano-bentonite
Compatibility between polyformaldehyde, and make nano-bentonite disperse evenly, to make nano-bentonite to polyformaldehyde in polyformaldehyde
Creep resistance humidification it is more preferable, also made by controlling the degree of polymerization of polyformaldehyde modified material modified in creep resistance
Reach optimum balance relation between processability, it is material modified in the condition with excellent creep resistance so as to make to obtain
Under, it may have excellent processability, it is applied in more areas.
A kind of above-mentioned polyformaldehyde creep resistant is material modified, wherein, described nano-bentonite particle diameter is 10-80nm；Nanometer
Bentonite particle diameter is smaller, and dispersiveness is poorer, and nano-bentonite particle diameter is bigger, poorer to the creep resistant humidification of polyformaldehyde；It is excellent
Choosing, described nano-bentonite particle diameter is 30-50nm；Most preferably, described nano-bentonite particle diameter is 40nm.
A kind of above-mentioned polyformaldehyde creep resistant is material modified, wherein, described modifying agent is triacetyl glycerine and mercaptan first
The mixture of Ji Xi compositions；Described modifying agent can improve the compatibility of nano-bentonite and polyformaldehyde, and and can is swollen in nanometer
Moisten native surface and form polar group, beneficial to scattered；Preferably, triacetyl glycerine and thiol methyl tin in described modifying agent
The ratio between amount of material is 1 ︰ 1.
A kind of above-mentioned polyformaldehyde creep resistant is material modified, wherein, the degree of polymerization of nitrile rubber is bigger, then is crosslinked post-modification material
The creep resistance of material is poorer, and processability is better, and the polymer of nitrile rubber is smaller, then the creep resistance for being crosslinked post-modification material is got over
Good, processability is poorer, therefore, selects the rational nitrile rubber degree of polymerization, is the important means for balancing creep resistance and processability.
The degree of polymerization of described nitrile rubber is 120-200；Preferably, the degree of polymerization of described nitrile rubber is 140-180；It is optimal
, the degree of polymerization of described nitrile rubber is 160；By preferred, obtain it is material modified both there is excellent creep resistance,
With preferable processability, it is adapted to the application in more areas.
Wherein, the described polyformaldehyde degree of polymerization is 500-900；Preferably, the degree of polymerization of the polyformaldehyde is 600-800；
Most preferably, the degree of polymerization of described polyformaldehyde is 700；By preferred, what is obtained material modified both has excellent creep resistant
Property, it may have preferable processability.
A kind of above-mentioned polyformaldehyde creep resistant is material modified, wherein, described coupling agent is the isopropyl ester coupling agent of aluminic acid three；Aluminium
Sour three isopropyl esters can increase the compatibility between nano-bentonite and polyformaldehyde and modifying agent, improve material modified performance.
Wherein, described crosslinking agent is trimethoxy silane, and the crosslinking agent can be former by the polymer of two kinds of different polymerization degrees
Material is suitably crosslinked, and improves material modified creep resistance.
A kind of above-mentioned polyformaldehyde creep resistant is material modified, wherein, its raw material also includes dispersant, plasticizer, antistatic
One or more auxiliary agents in agent, coloring agent, brightener；Above-mentioned auxiliary agent can improve material modified processability, increase its work(
The effects such as energy property, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of polyformaldehyde creep resistant is material modified
Preparation method, 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 polyformaldehyde in the electric field, obtains compound；
（4）Combined Processing is being carried out after compound is well mixed with nitrile rubber, crosslinking agent, polyacrylamide, is obtaining poly- first
Aldehyde creep resistant is material modified.
A kind of material modified preparation method of polyformaldehyde creep resistant, is first carried out at coupling with coupling agent to nano-bentonite
Reason, increase nano-bentonite and modifying agent, the compatibility of polyformaldehyde；Processing is modified to nano-bentonite with modifying agent again,
And form polar group on its surface；Finally make the polar group pole in nano-bentonite surface and focused beam-forming using external electric field
Change, it is powered,, also can be with polyformaldehyde while making nano-bentonite dispersed by repelling each other between electric charge or attracting principle
Polar group on chain is bonded, so that the creep resistant enhancing effect of nano-bentonite is farthest embodied, so as to get
Modified polyacetal creep resistance significantly improve；The preparation method is simple and reliable, and it is material modified to be suitable for polyformaldehyde creep resistant
Extensive, industrialized production.
A kind of material modified preparation method of above-mentioned polyformaldehyde creep resistant, wherein, it is preferred that step 1 carries out coupling processing
During can use ultrasonic assistant；Shaken by the high speed of ultrasonic wave, make nano-bentonite dispersiveness more preferable, and to coupling at
Reason has facilitation.
A kind of material modified preparation method of above-mentioned polyformaldehyde creep resistant, 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-bentonite, improves modified polyacetal
Creep resistance.
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 to strand and it is bonded have an impact, material modified performance may be reduced；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, the material modified species for targetedly screening modifying agent, coupling agent and crosslinking agent of the present invention, nano-bentonite is made with gathering
Compatibility between formaldehyde is more preferable, and the dispersiveness in polyformaldehyde is more preferable, creep resistance enhancing of the nano-bentonite to polyformaldehyde
Effect is more preferable.
2nd, the present invention it is material modified made by controlling the degree of polymerization of polyformaldehyde and nitrile rubber it is modified material modified
Reach optimum balance relation between creep resistance and processability, so as to get it is material modified with excellent creep resistance
Under the conditions of, it may have excellent processability.
3rd, the material modified preparation method of the present invention, using the polarization of external electric field, nano-bentonite can be promoted poly-
Scattered and bonded in formaldehyde systems, the creep resistant enhancing effect of nano-bentonite is more preferable, obtained material modified creep resistant
Property is higher.
4th, the material modified preparation method of the present invention is simple, reliable, be adapted to polyformaldehyde creep resistant it is material modified it is extensive,
Industrialized 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）12 parts of nano-bentonite is handled with 0.5 part of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is wrapped with 2 parts of triacetyl glycerine and 2 parts of thiol methyl tin
Cover processing；
（3）It is in electric-field intensity after nano-bentonite after cladding is well mixed with the polyformaldehyde that 55 parts of the degree of polymerization is 700
Extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtain compound；
（4）Nitrile rubber that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 160,4 parts of trimethoxy silanes, 12 parts
Polyacrylamide it is well mixed after extruded, it is material modified to obtain polyformaldehyde creep resistant.
Embodiment 2
（1）10 parts of nano-bentonite is handled with 0.3 part of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is entered with 1.5 parts of triacetyl glycerine and 1.5 parts of thiol methyl tin
The processing of row cladding；
（3）In electric-field intensity after nano-bentonite after cladding is well mixed with the polyformaldehyde that 50 parts of the degree of polymerization is 500
To be extruded in 1.5kv/m electric field, compound is obtained；
（4）Nitrile rubber that the compound that step 3 is obtained and 15 parts of the degree of polymerization are 120,3 parts of trimethoxy silanes, 10 parts
Polyacrylamide it is well mixed after extruded, it is material modified to obtain polyformaldehyde creep resistant.
Embodiment 3
（1）15 parts of nano-bentonite is handled with 0.6 part of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is entered with 2.5 parts of triacetyl glycerine and 2.5 parts of thiol methyl tin
The processing of row cladding；
（3）In electric-field intensity after nano-bentonite after cladding is well mixed with the polyformaldehyde that 60 parts of the degree of polymerization is 900
To be extruded in the constant parallel electric field of 2.5kv/m direction of an electric field, compound is obtained；
（4）Nitrile rubber that the compound that step 3 is obtained and 25 parts of the degree of polymerization are 200,5 parts of trimethoxy silanes, 15 parts
Polyacrylamide it is well mixed after extruded, it is material modified to obtain polyformaldehyde creep resistant.
Comparative example 1
（1）12 parts of nano-bentonite is handled with 0.5 part of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment and 5 parts of dispersant, the polyformaldehyde that 55 parts of the degree of polymerization is 700 are mixed
Extruded after closing uniformly in the constant parallel electric field of the direction of an electric field that electric-field intensity is 2.0kv/m, obtain compound；
（3）Nitrile rubber that the compound that step 2 is obtained and 20 parts of the degree of polymerization are 160,4 parts of trimethoxy silanes, 12 parts
Polyacrylamide it is well mixed after extruded, obtain material modified.
Comparative example 2
（1）12 parts of nano-bentonite is handled with 0.5 part of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is wrapped with 2 parts of triacetyl glycerine and 2 parts of thiol methyl tin
Cover processing；
（3）The fourth for being 160 by polyformaldehyde that the nano-bentonite after cladding and 55 parts of the degree of polymerization are 700,20 parts of the degree of polymerization
Extruded, obtained material modified after nitrile rubber, 4 parts of trimethoxy silanes, 12 parts of polyacrylamide are well mixed.
Comparative example 3
（1）12 parts of nano-bentonite is handled with 0.5 part 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 nitrile rubber and 2 parts of thiol methyl tin
Reason；
（3）It is in electric-field intensity after nano-bentonite after cladding is well mixed with the polyformaldehyde that 55 parts of the degree of polymerization is 700
Extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtain compound；
（4）Nitrile rubber that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 160,4 parts of trimethoxy silanes, 12 parts
Polyacrylamide it is well mixed after extruded, obtain material modified.
Comparative example 4
（1）12 parts of nano-bentonite is handled with 0.5 part of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is wrapped with 2 parts of triacetyl glycerine and 2 parts of thiol methyl tin
Cover processing；
（3）By nitrile rubber that the nano-bentonite after cladding and 20 parts of the degree of polymerization are 160,4 parts of trimethoxy silanes, 12 parts
Polyacrylamide, 55 parts of the degree of polymerization be 700 polyformaldehyde it is well mixed after be 2.0kv/m in electric-field intensity direction of an electric field
Extruded, obtained material modified in constant parallel electric field.
Comparative example 5
（1）12 parts of nano-bentonite is handled with 0.5 part of the isopropyl ester of aluminic acid three；
（2）Nano-bentonite Jing Guo coupling agent treatment is wrapped with 2 parts of triacetyl glycerine and 2 parts of thiol methyl tin
Cover processing；
（3）It is in electric-field intensity after nano-bentonite after cladding is well mixed with the polyformaldehyde that 55 parts of the degree of polymerization is 400
Extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtain compound；
（4）Nitrile rubber that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 100,12 parts of polyacrylamide, 4 parts
Extruded, obtained material modified after trimethoxy silane is well mixed.
Will be material modified 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.
Above-mentioned analysis of experimental data is understood, the polyformaldehyde creep resistant of the present invention being prepared in embodiment 1-3 is modified material
Material, nano-bentonite are uniformly dispersed, and good with the compatibility of polyformaldehyde, material modified creep resistance is good, and processability is good；And comparative example
In 1, modifying agent is not used processing is modified to nano-bentonite, although adding dispersant, the scattered effect of nano-bentonite
Fruit is poor, and the poor compatibility with polyformaldehyde, material modified creep resistance significantly reduces；Do not answered in the electric field in comparative example 2
Conjunction is handled, and nano-bentonite dispersion effect is poor, and material modified creep resistance significantly reduces；Modifying agent is not this in comparative example 3
Apply for defined, nano-bentonite dispersion effect is poor, and material modified creep resistance significantly reduces；It is crosslinked in comparative example 4 anti-
Equally should carry out in the electric field, electric field has a negative impact to cross-linking reaction, so as to get material modified creep resistance reduce；
The polyformaldehyde and the nitrile rubber degree of polymerization used in comparative example 5 is too small, although creep resistance increased after compound, it is processed
Property significantly reduces, and is unfavorable for material modified application.
Claims (10)
1. a kind of polyformaldehyde creep resistant is material modified, it is characterised in that is prepared including following parts by weight raw material：50-60
The polyformaldehyde of part, the nano-bentonite of 10-15 parts, the modifying agent of 3-5 parts, the nitrile rubber of 15-25 parts, the idol of 0.3-0.6 parts
Join agent, the crosslinking agent of 3-5 parts, the polyacrylamide of 10-15 parts；The modifying agent is triacetyl glycerine and thiol methyl tin group
Into mixture；The coupling agent is the isopropyl ester coupling agent of aluminic acid three, and the crosslinking agent is trimethoxy silane；The butyronitrile rubber
The degree of polymerization of glue is 120-200；The polyformaldehyde degree of polymerization is 500-900.
It is 2. according to claim 1 material modified, it is characterised in that triacetyl glycerine and mercaptan first in the modifying agent
The ratio between amount of material of base tin is 1 ︰ 1.
It is 3. according to claim 1 material modified, it is characterised in that the degree of polymerization of the nitrile rubber is 140-180.
It is 4. according to claim 3 material modified, it is characterised in that the degree of polymerization of the nitrile rubber is 160.
It is 5. according to claim 1 material modified, it is characterised in that the polyformaldehyde degree of polymerization is 600-800.
It is 6. according to claim 5 material modified, it is characterised in that the polyformaldehyde degree of polymerization is 700.
7. a kind of material modified preparation method as described in claim any one of 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 polyformaldehyde in the electric field, obtains compound；
（4）By compound and nitrile rubber, crosslinking agent, polyacrylamide, be well mixed after carrying out Combined Processing, obtain poly- first
Aldehyde creep resistant is material modified.
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 |
|---|---|---|---|
| CN201711270650.8A CN107759968A (en) | 2017-12-05 | 2017-12-05 | A kind of polyformaldehyde creep resistant is material modified and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711270650.8A CN107759968A (en) | 2017-12-05 | 2017-12-05 | A kind of polyformaldehyde creep resistant is material modified and preparation method thereof |
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| CN107759968A true CN107759968A (en) | 2018-03-06 |
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Application publication date: 20180306 |