CN107936523A - A kind of chlorinated polyether heat resist modification material and preparation method thereof - Google Patents
A kind of chlorinated polyether heat resist modification material and preparation method thereof Download PDFInfo
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- CN107936523A CN107936523A CN201711244378.6A CN201711244378A CN107936523A CN 107936523 A CN107936523 A CN 107936523A CN 201711244378 A CN201711244378 A CN 201711244378A CN 107936523 A CN107936523 A CN 107936523A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Abstract
The invention discloses a kind of chlorinated polyether heat resist modification material and preparation method thereof, including following parts by weight raw material to be prepared：25 parts of nano-aluminum hydroxide, 1.2 2.0 parts of modifying agent, 10 15 parts of polyvinyl chloride, 55 75 parts of chlorinated polyether, 0.3 0.8 parts of coupling agent, 0.1 0.3 parts of crosslinking agent, 0.1 0.3 parts of sebacic acid dibutyl ester, 0.1 0.3 parts of zinc stearate；The present invention is for composite by the nano-aluminum hydroxide Jing Guo specific aim modification and chlorinated polyether, and nano-aluminum hydroxide is set to be dispersed in chlorinated polyether system, obtained modified material resistance to elevated temperatures is excellent, is conducive to application of the chlorinated polyether in more areas.
Description
Technical field
The present invention relates to modified material field, and in particular to a kind of chlorinated polyether heat resist modification material and its preparation side
Method.
Background technology
Chlorinated polyether chemical name is double (chloromethyl) fourth oxygen rings of poly- 3,3'-, is by double (chloromethyl) fourth oxygen ring lists of 3,3'-
Ring-opening polymerisation is made body in the presence of a catalyst.Chlorinated polyether has higher heat resistance, chemical resistance and wearability, and
Water imbibition is small, and mechanical performance is high, its product is widely used in machinery, electronics, chemical industry, medical instrument, household utensils, office accommodation
Etc..
With the continuous improvement that people require material resistance to elevated temperatures, the chlorinated polyether without heat resist modification has been difficult to
Meet demand, thus, heat resist modification is carried out to chlorinated polyether and is necessitated.Now to the heat resist modification processing method of ABS
Species is various, and modified effect is also fine, especially with the appearance and application of nano material, the heat-resisting quantity increase of chlorinated polyether
Significant effect, enables chlorinated polyether largely to be used in more areas, but there is also deficiency.Although nano material increases with high temperature resistant
The advantages of potent fruit is good, and additive amount is small, but there is also difficulties in dispersion, it is of high cost the defects of.During heat resist modification is carried out,
Nano material, which disperses inequality, can influence its high-temperature resistant result, and obtained modified material heat-resisting quantity is relatively low, the life to modified material
Production and application adversely affect.
The content of the invention
The defects of it is an object of the invention to overcome existing modified material heat-resisting quantity poor, there is provided a kind of chlorinated polyether is resistance to
High temperature modified material and preparation method thereof；The present invention by the nano-aluminum hydroxide Jing Guo specific aim modification and chlorinated polyether into
Row is compound, and nano-aluminum hydroxide is dispersed in chlorinated polyether system, and obtained modified material resistance to elevated temperatures is excellent,
Be conducive to application of the chlorinated polyether in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of chlorinated polyether heat resist modification material, including it is following
Parts by weight raw material are prepared：2-5 parts of nano-aluminum hydroxide, 1.2-2.0 parts of modifying agent, 10-15 parts of polyvinyl chloride,
55-75 parts of chlorinated polyether, 0.3-0.8 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 0.1-0.3 parts of sebacic acid two are pungent
Fat, 0.1-0.3 parts of zinc stearate.
A kind of above-mentioned chlorinated polyether heat resist modification material, it is resistance to increase resin material according to nano-aluminum hydroxide and crosslinking
High temperatures basic principle, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve a nanometer hydrogen
Compatibility between aluminium oxide and chlorinated polyether, and make nano-aluminum hydroxide disperse evenly, to make a nanometer hydrogen in chlorinated polyether
Aluminium oxide is more preferable to the heat-resisting quantity humidification of chlorinated polyether, is also made by controlling the degree of polymerization of chlorinated polyether modified
Modified material reaches optimum balance relation between heat-resisting quantity and processability, so that the modified material made is with excellent
Heat-resisting quantity under conditions of, it may have excellent processability, allows it to be applied in more areas.
A kind of above-mentioned chlorinated polyether heat resist modification material, wherein, the nano-aluminum hydroxide particle diameter is 10-80nm；
Nano-aluminum hydroxide particle diameter is smaller, and dispersiveness is poorer, and nano-aluminum hydroxide particle diameter is bigger, strengthens work to the high temperature resistant of chlorinated polyether
With poorer；Preferably, the nano-aluminum hydroxide particle diameter is 30-50nm；Most preferably, the nano-aluminum hydroxide particle diameter
For 40nm.
A kind of above-mentioned chlorinated polyether heat resist modification material, wherein, the modifying agent is di (isooctyl) phosphate and epoxy
The mixture of chloropropane composition；The modifying agent can improve nano-aluminum hydroxide and chlorinated polyether compatibility and
Nano-aluminum hydroxide surface forms polar group, beneficial to scattered；Preferably, di (isooctyl) phosphate and epoxy in the modifying agent
The ratio between amount of material of chloropropane is 1 ︰ 1.
A kind of above-mentioned chlorinated polyether heat resist modification material, wherein, the degree of polymerization of polyvinyl chloride is bigger, then is crosslinked post-modification
The heat-resisting quantity of material is poorer, and processability is better, and the polymer of polyvinyl chloride is smaller, then is crosslinked the heat-resisting quantity of post-modification material
Better, processability is poorer, therefore, selects rational polyvinyl chloride polymerization degree, is the important hand for balancing heat-resisting quantity and processability
Section.The degree of polymerization of the polyvinyl chloride is 280-380；Preferably, the degree of polymerization of the polyvinyl chloride is 300-350；Most
Excellent, the degree of polymerization of the polyvinyl chloride is 320；By preferred, obtained modified material both has excellent heat-resisting quantity,
Also there is preferable processability, be adapted to the application in more areas.
Wherein, the chlorinated polyether degree of polymerization is 600-1000；Preferably, the degree of polymerization of the chlorinated polyether is 700-
900；Most preferably, the degree of polymerization of the chlorinated polyether is 800；By preferred, obtained modified material had both had excellent
Heat-resisting quantity, it may have preferable processability.
A kind of above-mentioned chlorinated polyether heat resist modification material, wherein, the coupling agent is aluminate coupling agent；Aluminate
The compatibility between nano-aluminum hydroxide and chlorinated polyether and modifying agent can be increased, improve the performance of modified material.
Wherein, the crosslinking agent is metachloroperbenzoic acid, which can be by the polymer of two kinds of different polymerization degrees
Raw material are suitably crosslinked, and have facilitation to the heat-resisting quantity for improving modified material.
A kind of above-mentioned chlorinated polyether heat resist modification material, wherein, its raw material further includes dispersant, plasticizer, anti-quiet
One or more auxiliary agents in electric agent, coloring agent, brightener；Above-mentioned auxiliary agent can improve the processability of modified material, increase it
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 chlorinated polyether heat resist modification material
The preparation method of material, comprises the following steps：
（1）Nano-aluminum hydroxide is handled with coupling agent；
（2）Nano-aluminum hydroxide Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-aluminum hydroxide after cladding and chlorinated polyether processing for composite in the electric field after mixing, mixed
Close material；
（4）By mixture and polyvinyl chloride, crosslinking agent, zinc stearate, sebacic acid dibutyl ester after mixing at place for composite
Reason, obtains chlorinated polyether heat resist modification material.
A kind of preparation method of chlorinated polyether heat resist modification material, is first coupled nano-aluminum hydroxide with coupling agent
Processing, increase nano-aluminum hydroxide and modifying agent, the compatibility of chlorinated polyether；Nano-aluminum hydroxide is changed with modifying agent again
Property processing, and its surface formed polar group；Finally made using external electric field in nano-aluminum hydroxide surface and chlorinated polyether chain
Polar group polarization, it is powered, by repelling each other between electric charge or attracting principle, make dispersed same of nano-aluminum hydroxide
When, also can be bonded with the polar group on chlorinated polyether chain, so that the high temperature resistant enhancing effect of nano-aluminum hydroxide obtains most
The embodiment of big degree, so as to get modified chlorinated polyethers heat-resisting quantity significantly improve；The preparation method is simple and reliable, is suitable for
Extensive, the industrialized production of chlorinated polyether heat resist modification material.
A kind of preparation method of above-mentioned chlorinated polyether heat resist modification material, wherein, it is preferred that step 1 is carried out at coupling
Ultrasonic wave can be used to aid in during reason；Shaken by the high speed of ultrasonic wave, make nano-aluminum hydroxide dispersiveness more preferable, and antithesis
Connection processing has facilitation.
A kind of preparation method of above-mentioned chlorinated polyether heat resist modification material, wherein, the electric field energy described in step 3 is to base
Group produces polarization, makes group powered, so as to promote the scattered and bonded effect of nano-aluminum hydroxide, improves modified chlorinated
The heat-resisting quantity of polyethers.
Preferably, the electric field strength is 0.5-2kv/m；Electric field strength is too small, and polarization effect is weak, to nanometer hydroxide
The dispersion effect of aluminium 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 performance for having an impact, may be decreased modified material to strand；Most preferably, the electric field strength is
0.8-1.5kv/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, and the scattered and bonded promotion to nano-aluminum hydroxide is made
Use best results.
Compared with prior art, beneficial effects of the present invention：
1st, modified material of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, make nano-aluminum hydroxide with
Compatibility between chlorinated polyether is more preferable, and the dispersiveness in chlorinated polyether is more preferable, and nano-aluminum hydroxide is to the resistance to of chlorinated polyether
High temperatures humidification is more preferable.
2nd, modified material of the present invention makes modified modification material by controlling the degree of polymerization of chlorinated polyether and polyvinyl chloride
Material reach optimum balance relation between heat-resisting quantity and processability, so as to get modified material with excellent heat-resisting quantity
Under conditions of, it may have excellent processability.
3rd, the preparation method of modified material of the present invention, using the polarization of external electric field, can promote nano-aluminum hydroxide to exist
Scattered and bonded in chlorinated polyether system, the high temperature resistant enhancing effect of nano-aluminum hydroxide is more preferable, obtained modified material
Heat-resisting quantity higher.
4th, the preparation method of modified material of the present invention is simple, reliable, is adapted to the big rule of chlorinated polyether heat resist modification material
Mould, 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）3 parts of nano-aluminum hydroxide is handled with 0.6 part of Aluminate；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 0.8 part of di (isooctyl) phosphate and 0.8 part of epoxychloropropane
Carry out cladding processing；
（3）By chlorinated polyether that the nano-aluminum hydroxide after cladding and 65 parts of the degree of polymerization are 800 after mixing in electric-field strength
Spend to be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Polyvinyl chloride that the mixture that step 3 is obtained and 12 parts of the degree of polymerization are 320,0.2 part of metachloroperbenzoic acid,
0.2 part of sebacic acid dibutyl ester, 0.2 part of zinc stearate are extruded after mixing, obtain chlorinated polyether heat resist modification
Material.
Embodiment 2
（1）2 parts of nano-aluminum hydroxide is handled with 0.3 part of Aluminate；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 0.6 part of di (isooctyl) phosphate and 0.6 part of epoxychloropropane
Carry out cladding processing；
（3）By chlorinated polyether that the nano-aluminum hydroxide after cladding and 55 parts of the degree of polymerization are 1000 after mixing in electric field
Intensity is to be extruded in the electric field of 2.0kv/m, obtains mixture；
（4）Polyvinyl chloride that the mixture that step 3 is obtained and 10 parts of the degree of polymerization are 280,0.3 part of metachloroperbenzoic acid,
0.1 part of sebacic acid dibutyl ester, 0.3 part of zinc stearate are extruded after mixing, obtain chlorinated polyether heat resist modification
Material.
Embodiment 3
（1）5 parts of nano-aluminum hydroxide is handled with 0.8 part of Aluminate；
（2）Nano-aluminum hydroxide Jing Guo coupling agent treatment is carried out with 1 part of di (isooctyl) phosphate and 1 part of epoxychloropropane
Cladding processing；
（3）By chlorinated polyether that the nano-aluminum hydroxide after cladding and 75 parts of the degree of polymerization are 600 after mixing in electric field
Intensity is to be extruded in the constant parallel electric field of the direction of an electric field of 0.5kv/m, obtains mixture；
（4）Polyvinyl chloride that the mixture that step 3 is obtained and 15 parts of the degree of polymerization are 380,0.1 part of metachloroperbenzoic acid,
0.3 part of sebacic acid dibutyl ester, 0.1 part of zinc stearate are extruded after mixing, obtain chlorinated polyether heat resist modification
Material.
Comparative example 1
（1）3 parts of nano-aluminum hydroxide is handled with 0.6 part of Aluminate；
（2）Nano-aluminum hydroxide Jing Guo coupling agent treatment and 3 parts of dispersant, the chlorination that 65 parts of the degree of polymerization is 800 are gathered
Ether is extruded in the constant parallel electric field of the direction of an electric field that electric field strength is 1.2kv/m after mixing, obtains mixture；
（3）Polyvinyl chloride that the mixture that step 2 is obtained and 12 parts of the degree of polymerization are 320,0.2 part of metachloroperbenzoic acid,
0.2 part of sebacic acid dibutyl ester, 0.2 part of zinc stearate are extruded after mixing, obtain modified material.
Comparative example 2
（1）3 parts of nano-aluminum hydroxide is handled with 0.6 part of Aluminate；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 0.8 part of di (isooctyl) phosphate and 0.8 part of epoxychloropropane
Carry out cladding processing；
（3）It is 320 by chlorinated polyether that the nano-aluminum hydroxide after cladding and 65 parts of the degree of polymerization are 800,12 parts of the degree of polymerization
Polyvinyl chloride, 0.2 part of metachloroperbenzoic acid, 0.2 part of sebacic acid dibutyl ester, 0.2 part of zinc stearate after mixing
Extruded, obtain modified material.
Comparative example 3
（1）3 parts of nano-aluminum hydroxide is handled with 0.6 part of Aluminate；
（2）Nano-aluminum hydroxide Jing Guo coupling agent treatment is carried out with 0.8 part of polystyrene and 0.8 part of epoxychloropropane
Cladding processing；
（3）By chlorinated polyether that the nano-aluminum hydroxide after cladding and 65 parts of the degree of polymerization are 800 after mixing in electric-field strength
Spend to be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Polyvinyl chloride that the mixture that step 3 is obtained and 12 parts of the degree of polymerization are 320,0.2 part of metachloroperbenzoic acid,
0.2 part of sebacic acid dibutyl ester, 0.2 part of zinc stearate are extruded after mixing, obtain modified material.
Comparative example 4
（1）3 parts of nano-aluminum hydroxide is handled with 0.6 part of Aluminate；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 0.8 part of di (isooctyl) phosphate and 0.8 part of epoxychloropropane
Carry out cladding processing；
（3）By the polyvinyl chloride of the nano-aluminum hydroxide after cladding and 12 parts of the degree of polymerization for 320,0.2 part of m-chloro peroxide benzene first
Acid, 0.2 part sebacic acid dibutyl ester, 0.2 part of zinc stearate, 65 parts of the degree of polymerization be 800 chlorinated polyether after mixing
Extruded in the constant parallel electric field of the direction of an electric field that electric field strength is 1.2kv/m, obtain modified material.
Comparative example 5
（1）3 parts of nano-aluminum hydroxide is handled with 0.6 part of Aluminate；
（2）By the nano-aluminum hydroxide Jing Guo coupling agent treatment 0.8 part of di (isooctyl) phosphate and 0.8 part of epoxychloropropane
Carry out cladding processing；
（3）By chlorinated polyether that the nano-aluminum hydroxide after cladding and 65 parts of the degree of polymerization are 500 after mixing in electric-field strength
Spend to be extruded in the constant parallel electric field of the direction of an electric field of 1.2kv/m, obtain mixture；
（4）Polyvinyl chloride that the mixture that step 3 is obtained and 12 parts of the degree of polymerization are 250,0.2 part of sebacic acid dibutyl ester,
0.2 part of zinc stearate, 0.2 part of metachloroperbenzoic acid are extruded after mixing, obtain modified material.
By the modified material in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data are as follows：
| Performance | Fusing point（℃） | Processability |
| Embodiment 1 | 192 | ++++ |
| Embodiment 2 | 191 | ++++ |
| Embodiment 3 | 192 | ++++ |
| Comparative example 1 | 183 | ++++ |
| Comparative example 2 | 186 | ++++ |
| Comparative example 3 | 188 | ++++ |
| Comparative example 4 | 187 | ++++ |
| Comparative example 5 | 192 | ++ |
| Pure chlorinated polyether | 176 | +++++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the chlorinated polyether heat resist modification of the present invention being prepared in embodiment 1-3
Material, nano-aluminum hydroxide are uniformly dispersed, and good with the compatibility of chlorinated polyether, modified material heat-resisting quantity is good, and processability is good；And
In comparative example 1, modifying agent is not used processing is modified to nano-aluminum hydroxide, although adding dispersant, nanometer hydrogen-oxygen
Change aluminium dispersion effect is poor, and the poor compatibility with chlorinated polyether, the heat-resisting quantity of modified material significantly reduces；Do not exist in comparative example 2
Processing for composite in electric field, nano-aluminum hydroxide dispersion effect is poor, and the heat-resisting quantity of modified material significantly reduces；Comparative example 3
Middle modifying agent is not the application defined, and nano-aluminum hydroxide dispersion effect is poor, and the heat-resisting quantity of modified 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 modified material
Heat-resisting quantity reduce；The chlorinated polyether and polyvinyl chloride polymerization used in comparative example 5 spend it is small, although it is compound after heat-resisting quantity
It increased, but its processability significantly reduces, and is unfavorable for the application of modified material.
Claims (10)
1. a kind of chlorinated polyether heat resist modification material, it is characterised in that be prepared including following parts by weight raw material：2-5
The nano-aluminum hydroxide, 1.2-2.0 parts of modifying agent, 10-15 parts of polyvinyl chloride, 55-75 parts of chlorinated polyether, 0.3- of part
0.8 part of coupling agent, 0.1-0.3 parts of crosslinking agent, 0.1-0.3 parts of sebacic acid dibutyl ester, 0.1-0.3 parts of zinc stearate；
The mixture that the modifying agent forms for di (isooctyl) phosphate with epoxychloropropane；The coupling agent is aluminate coupling agent, institute
It is metachloroperbenzoic acid to state crosslinking agent；The degree of polymerization of the polyvinyl chloride is 280-380；The chlorinated polyether degree of polymerization is
600-1000。
2. modified material according to claim 1, it is characterised in that di (isooctyl) phosphate and epoxy chlorine in the modifying agent
The ratio between amount of material of propane is 1 ︰ 1.
3. modified material according to claim 1, it is characterised in that the degree of polymerization of the polyvinyl chloride is 300-350.
4. modified material according to claim 3, it is characterised in that the degree of polymerization of the polyvinyl chloride is 320.
5. modified material according to claim 1, it is characterised in that the chlorinated polyether degree of polymerization is 700-900.
6. modified material according to claim 5, it is characterised in that the chlorinated polyether degree of polymerization is 800.
7. a kind of preparation method of the modified material as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nano-aluminum hydroxide is handled with coupling agent；
（2）Nano-aluminum hydroxide Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）By the nano-aluminum hydroxide after cladding and chlorinated polyether processing for composite in the electric field after mixing, mixed
Close material；（4）By mixture and polyvinyl chloride, crosslinking agent, zinc stearate, sebacic acid dibutyl ester after mixing at place for composite
Reason, obtains chlorinated polyether heat resist modification material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric field strength is 0.5-2kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric field strength is 0.8-1.5kv/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.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117123A (en) * | 2019-12-27 | 2020-05-08 | 天津永高塑业发展有限公司 | CPVC chemical pipeline material with high thermal conductivity and high wear resistance and preparation method thereof |
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2017
- 2017-11-30 CN CN201711244378.6A patent/CN107936523A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117123A (en) * | 2019-12-27 | 2020-05-08 | 天津永高塑业发展有限公司 | CPVC chemical pipeline material with high thermal conductivity and high wear resistance and preparation method thereof |
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Application publication date: 20180420 |