CN108047660A - A kind of polyethylene terephthalate modified material and preparation method thereof - Google Patents
A kind of polyethylene terephthalate modified material and preparation method thereof Download PDFInfo
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- CN108047660A CN108047660A CN201711270615.6A CN201711270615A CN108047660A CN 108047660 A CN108047660 A CN 108047660A CN 201711270615 A CN201711270615 A CN 201711270615A CN 108047660 A CN108047660 A CN 108047660A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of polyethylene terephthalate modified materials and preparation method thereof, are prepared including following parts by weight raw material：60 70 parts of polyethylene terephthalate, 15 20 parts of nano barium sulfate, 58 parts of modifying agent, 15 25 parts of butadiene rubber, 0.3 0.5 parts of coupling agent, 0.1 0.3 parts of crosslinking agent, 13 parts of barium stearate；The present invention carries out the nano barium sulfate Jing Guo specific aim modification with polyethylene terephthalate compound, and nano barium sulfate is made to be dispersed in polyethylene terephthalate system, obtained modified material excellent shock resistance is conducive to application of the polyethylene terephthalate in more areas.
Description
Technical field
The present invention relates to modified material fields, and in particular to a kind of polyethylene terephthalate modified material and its preparation
Method.
Background technology
Polyethylene terephthalate be exchanged by dimethyl terephthalate (DMT) with glycol ester or with terephthalic acid (TPA) with
Ethylene glycol esterification first synthesizes bishydroxyethyl terephthalate, then carries out polycondensation reaction again and is made, and belongs to crystal type saturated polyester, is
Milky or light yellow, highly crystalline polymer.With excellent mechanical performance, rigidity is high, hardness is big, and water imbibition is small, ruler
Very little stability is good, good toughness, impact resistance, rub resistance, creep resistance, and chemical resistance is good.In industries such as automobile, aviation, electronics, machineries
In be used widely.
With the continuous improvement that people require material shock resistance, the poly terephthalic acid second without impact modification
Diester has been difficult to meet demand, thus, impact modification is carried out to polyethylene terephthalate and is necessitated.Now to poly- pair
The impact modification processing method species of polyethylene terephthalate is various, and modified effect is also fine, especially with nano material
Appearance and application, the impact resistance of polyethylene terephthalate increases significant effect, enables polyethylene terephthalate
It is largely used in more areas, but there is also deficiencies.Although nano material has, shock resistance enhancing effect is good, small excellent of additive amount
Point, but there is also difficulties in dispersion, it is of high cost the defects of.During impact modification is carried out, nano material disperses uneven meeting shadow
Its shock resistance effect is rung, obtained modified material impact resistance is relatively low, and the production and application to modified material adversely affect.
The content of the invention
It the defects of it is an object of the invention to overcome existing polyethylene terephthalate materials impact resistance poor, provides
A kind of polyethylene terephthalate modified material and preparation method thereof；The present invention is by the nano-sulfur Jing Guo specific aim modification
Sour barium and polyethylene terephthalate progress are compound, and nano barium sulfate is made to be dispersed in polyethylene terephthalate body
In system, obtained modified material excellent shock resistance is conducive to application of the polyethylene terephthalate in more areas.
In order to realize foregoing invention purpose, the present invention provides a kind of polyethylene terephthalate modified material, including
Following parts by weight raw material are prepared：60-70 parts of polyethylene terephthalate, 15-20 parts of nano barium sulfate, 5-8
The modifying agent, 15-25 parts of butadiene rubber, 0.3-0.5 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of tristearin of part
Sour barium.
A kind of above-mentioned polyethylene terephthalate modified material can increase resin material according to nano barium sulfate and crosslinking
The basic principle of impact resistance, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nanometer
Compatibility between barium sulfate and polyethylene terephthalate, and nano barium sulfate is made to divide in polyethylene terephthalate
It dissipates evenly, makes nano barium sulfate more preferable to the impact resistance humidification of polyethylene terephthalate, it is also poly- by controlling
The degree of polymerization of ethylene terephthalate is put down modified modified material to be made to reach optimal between impact resistance and processability
Weighing apparatus relation, so as to which the modified material that makes is under conditions of with excellent impact resistance, it may have excellent processability makes
It can be applied in more areas.
A kind of above-mentioned polyethylene terephthalate modified material, wherein, the nano barium sulfate grain size is 10-
80nm；Nano barium sulfate grain size is smaller, and dispersiveness is poorer, and nano barium sulfate grain size is bigger, to polyethylene terephthalate
Shock resistance humidification is poorer；Preferably, the nano barium sulfate grain size is 15-25nm；Most preferably, the nano-sulfur
Sour granellae footpath is 40nm.
A kind of above-mentioned polyethylene terephthalate modified material, wherein, the modifying agent is tetrabutyl titanate with gathering
The mixture of ethoxylated polyhydric alcohol composition；The modifying agent can improve the compatible of nano barium sulfate and polyethylene terephthalate
Property, and polar group can be formed on nano barium sulfate surface, beneficial to scattered；Preferably, tetrabutyl titanate in the modifying agent
It is 1 ︰ 2 with the ratio between the amount of substance of polyether polyol.
A kind of above-mentioned polyethylene terephthalate modified material, wherein, the degree of polymerization of butadiene rubber is bigger, then after being crosslinked
The impact resistance of modified material is poorer, and processability is better, and the polymer of butadiene rubber is smaller, then is crosslinked the anti-impact of post-modification material
Hitting property is better, and processability is poorer, therefore, selects the rational butadiene rubber degree of polymerization, is the weight for balancing impact resistance and processability
Want means.The degree of polymerization of the butadiene rubber is 120-240；Preferably, the degree of polymerization of the butadiene rubber is 150-
200；Optimal, the degree of polymerization of the butadiene rubber is 180；By preferred, obtained modified material had both had excellent resist
Impact, it may have preferable processability is suitble to.
Wherein, the polyethylene terephthalate degree of polymerization is 800-1200；Preferably, the poly terephthalic acid
The degree of polymerization of second diester is 900-1100；Most preferably, the degree of polymerization of the polyethylene terephthalate is 1000；Pass through
It is preferred that obtained modified material both has excellent impact resistance, it may have preferable processability.
A kind of above-mentioned polyethylene terephthalate modified material, wherein, the coupling agent is monoalkoxytitanates
Coupling agent；Monoalkoxytitanates can increase compatible between nano barium sulfate and polyethylene terephthalate and modifying agent
Property improves the shock resistance of modified material.
Wherein, the crosslinking agent is ethylene glycol dimethacrylate, which can be by two kinds of different polymerization degrees
Polymer raw materials are suitably crosslinked, and improve the impact resistance of modified material.
A kind of above-mentioned polyethylene terephthalate modified material, wherein, raw material further include dispersant, plasticizer,
One or more auxiliary agents in antistatic agent, coloring agent, brightener；Above-mentioned auxiliary agent can improve the processability of modified material, increase
The effects that adding it functional, so as to increase its applicability.
In order to realize foregoing invention purpose, further, the present invention also provides a kind of polyethylene terephthalate to change
The preparation method of property material, comprises 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）Nano barium sulfate after cladding and polyethylene terephthalate are subjected to compound place in the electric field after mixing
Reason, obtains mixture；
（4）Mixture and butadiene rubber, crosslinking agent, barium stearate are being subjected to combined processing after mixing, obtained poly- to benzene
Dioctyl phthalate second diester modified material.
A kind of preparation method of polyethylene terephthalate modified material first carries out nano barium sulfate with coupling agent even
Connection processing, increases nano barium sulfate and modifying agent, the compatibility of polyethylene terephthalate；Again with modifying agent to nanometer sulfuric acid
Barium is modified processing, and is formed on its surface polar group；Finally make nano barium sulfate surface using external electric field and gather to benzene
Polar group polarization in dioctyl phthalate second diester chain, it is charged, by repelling each other between charge or attracting principle, make nano barium sulfate
, also can be bonded with the polar group on polyethylene terephthalate chain while homodisperse, so that nano barium sulfate
Shock resistance enhancing effect is embodied to the greatest extent, so as to get modification polyethylene terephthalate impact resistance significantly carry
It is high；The preparation method is simple and reliable, is suitable for extensive, the industrialized production of polyethylene terephthalate modified material.
A kind of preparation method of above-mentioned polyethylene terephthalate modified material, wherein, it is preferred that step 1 carries out idol
Ultrasonic wave auxiliary can be used in connection processing procedure；It is shaken by the high speed of ultrasonic wave, makes nano barium sulfate dispersiveness more preferable and right
Coupling processing has facilitation.
A kind of preparation method of above-mentioned polyethylene terephthalate modified material, wherein, the electric field energy described in step 3
Polarization is generated to group, makes group charged, so as to promote the scattered and bonded effect of nano barium sulfate, is improved modified poly-
The impact resistance of ethylene terephthalate.
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 generates displacement,
Arrangement and the bonded shock resistance for having an impact, may be decreased modified material to strand；Most preferably, the electric field
Intensity is 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, polyethylene terephthalate modified material of the present invention targetedly screens the kind of modifying agent, coupling agent and crosslinking agent
Class makes the compatibility between nano barium sulfate and polyethylene terephthalate more preferable, in polyethylene terephthalate
Dispersed more preferable, nano barium sulfate is more preferable to the impact resistance humidification of polyethylene terephthalate.
2nd, polyethylene terephthalate modified material of the present invention is by controlling polyethylene terephthalate and along fourth rubber
The degree of polymerization of glue makes the modified modified material reach optimum balance relation between impact resistance and processability, so as to get
Modified material is under conditions of with excellent impact resistance, it may have excellent processability.
3rd, the preparation method of polyethylene terephthalate modified material of the present invention, utilizes the polarization of external electric field, energy
Promote nano barium sulfate scattered and bonded in polyethylene terephthalate system, the shock resistance enhancing effect of nano barium sulfate
Fruit is more preferable, the impact resistance higher of obtained modified material.
4th, preparation method of the present invention is simple, reliable, is suitble to the extensive, industrial of polyethylene terephthalate modified material
Metaplasia is produced.
Specific embodiment
With reference to test example and specific 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 0.4 part of monoalkoxytitanates；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of tetrabutyl titanate and 4 parts of polyether polyol
Processing；
（3）By polyethylene terephthalate that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 1000 after mixing
It is squeezed out in the constant parallel electric field of the direction of an electric field that electric field strength is 2.5kv/m, obtains mixture；
（4）Butadiene rubber that the mixture that step 3 is obtained and 20 parts of the degree of polymerization are 180,0.2 part of dimethacrylate second two
Alcohol ester, 2 parts of barium stearate are squeezed out after mixing, obtain polyethylene terephthalate modified material.
Embodiment 2
（1）15 parts of nano barium sulfate is handled with 0.3 part of monoalkoxytitanates；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 4 parts of tetrabutyl titanate and 4 parts of polyether polyol
Processing；
（3）By polyethylene terephthalate that the nano barium sulfate after cladding and 60 parts of the degree of polymerization are 1200 after mixing
It is squeezed out in the electric field for being 1.5kv/m in electric field strength, obtains mixture；
（4）Butadiene rubber that the mixture that step 3 is obtained and 15 parts of the degree of polymerization are 240,0.3 part of dimethacrylate second two
Alcohol ester, 3 parts of barium stearate are squeezed out after mixing, obtain polyethylene terephthalate modified material.
Embodiment 3
（1）20 parts of nano barium sulfate is handled with 0.5 part of monoalkoxytitanates；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of tetrabutyl titanate and 3 parts of polyether polyol
Processing；
（3）By polyethylene terephthalate that the nano barium sulfate after cladding and 70 parts of the degree of polymerization are 800 after mixing
It is squeezed out in the constant parallel electric field of the direction of an electric field that electric field strength is 3.0kv/m, obtains mixture；
（4）Butadiene rubber that the mixture that step 3 is obtained and 25 parts of the degree of polymerization are 120,0.1 part of dimethacrylate second two
Alcohol ester, 1 part of barium stearate are squeezed out after mixing, obtain polyethylene terephthalate modified material.
Comparative example 1
（1）18 parts of nano barium sulfate is handled with 0.4 part of monoalkoxytitanates；
（2）By the nano barium sulfate Jing Guo coupling agent treatment and 5 parts of dispersant, 65 parts of the degree of polymerization be 1000 it is poly- to benzene two
Formic acid second diester is squeezed out in the constant parallel electric field of the direction of an electric field that electric field strength is 2.5kv/m after mixing, is obtained
To mixture；
（3）Butadiene rubber that the mixture that step 2 is obtained and 20 parts of the degree of polymerization are 180,0.2 part of dimethacrylate second two
Alcohol ester, 2 parts of barium stearate are squeezed out after mixing, obtain modified material.
Comparative example 2
（1）18 parts of nano barium sulfate is handled with 0.4 part of monoalkoxytitanates；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of tetrabutyl titanate and 4 parts of polyether polyol
Processing；
（3）By polyethylene terephthalate that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 1000,20 parts poly-
It is right be 180 butadiene rubber, 0.2 part of ethylene glycol dimethacrylate, 2 parts of barium stearate squeezed after mixing
Go out, obtain modified material.
Comparative example 3
（1）18 parts of nano barium sulfate is handled with 0.4 part of monoalkoxytitanates；
（2）Nano barium sulfate Jing Guo coupling agent treatment is carried out with 2 parts of polystyrene and 4 parts of polyether polyol at cladding
Reason；
（3）By polyethylene terephthalate that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 1000 after mixing
It is squeezed out in the constant parallel electric field of the direction of an electric field that electric field strength is 2.5kv/m, obtains mixture；
（4）Butadiene rubber that the mixture that step 3 is obtained and 20 parts of the degree of polymerization are 180,0.2 part of dimethacrylate second two
Alcohol ester, 2 parts of barium stearate are squeezed out after mixing, obtain modified material.
Comparative example 4
（1）18 parts of nano barium sulfate is handled with 0.4 part of monoalkoxytitanates；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of tetrabutyl titanate and 4 parts of polyether polyol
Processing；
（3）By the butadiene rubber of the nano barium sulfate after cladding and 20 parts of the degree of polymerization for 180,0.2 part of dimethacrylate second
Diol ester, 2 parts of barium stearate, 65 parts of the degree of polymerization be 1000 polyethylene terephthalate after mixing in electric-field strength
It spends to be squeezed out in the constant parallel electric field of the direction of an electric field of 2.5kv/m, obtains modified material.
Comparative example 5
（1）18 parts of nano barium sulfate is handled with 0.4 part of monoalkoxytitanates；
（2）Nano barium sulfate Jing Guo coupling agent treatment is coated with 2 parts of tetrabutyl titanate and 4 parts of polyether polyol
Processing；
（3）By polyethylene terephthalate that the nano barium sulfate after cladding and 65 parts of the degree of polymerization are 700 after mixing
It is squeezed out in the constant parallel electric field of the direction of an electric field that electric field strength is 2.5kv/m, obtains mixture；
（4）Butadiene rubber that the mixture that step 3 is obtained and 20 parts of the degree of polymerization are 100,2 parts of barium stearate, 0.2 part two
Methacrylic acid glycol ester is squeezed out after mixing, obtains 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 | Notch impact strength（KJ/m2） | Processability |
| Embodiment 1 | 53.6 | ++++ |
| Embodiment 2 | 52.8 | ++++ |
| Embodiment 3 | 53.4 | ++++ |
| Comparative example 1 | 35.8 | ++++ |
| Comparative example 2 | 41.4 | ++++ |
| Comparative example 3 | 43.8 | ++++ |
| Comparative example 4 | 46.2 | ++++ |
| Comparative example 5 | 53.7 | ++ |
| Polyethylene terephthalate | 5.2 | +++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the modified material of the present invention being prepared in embodiment 1-3, nano barium sulfate
It is uniformly dispersed, modified material good impact resistance good with the compatibility of polyethylene terephthalate, 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 polyethylene terephthalate, the impact resistance of modified material significantly reduce；Not in electricity in comparative example 2
Combined processing is carried out in, nano barium sulfate dispersion effect is poor, and the impact resistance of modified 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 material significantly reduces；Comparative example
Cross-linking reaction equally carries out in the electric field in 4, and electric field has a negative impact to cross-linking reaction, so as to get modified material anti-impact
Hitting property reduces；The polyethylene terephthalate 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 polyethylene terephthalate modified material.
Claims (10)
1. a kind of polyethylene terephthalate modified material, which is characterized in that be prepared including following parts by weight raw material：
60-70 parts of polyethylene terephthalate, 15-20 parts of nano barium sulfate, 5-8 parts of modifying agent, 15-25 parts of suitable fourth rubber
Glue, 0.3-0.5 parts of coupling agent, 0.1-0.3 parts of crosslinking agent, 1-3 parts of barium stearate；The modifying agent is tetrabutyl titanate
With the mixture of polyether polyol composition；The coupling agent is monoalkoxytitanates coupling agent, and the crosslinking agent is dimethyl
Acrylic acid glycol ester；The degree of polymerization of the butadiene rubber is 120-240；The polyethylene terephthalate degree of polymerization is
800-1200。
2. modified material according to claim 1, which is characterized in that tetrabutyl titanate and polyether polyols in the modifying agent
The ratio between amount of substance of alcohol is 1 ︰ 2.
3. modified material according to claim 1, which is characterized in that the degree of polymerization of the butadiene rubber is 150-200.
4. modified material according to claim 3, which is characterized in that the degree of polymerization of the butadiene rubber is 180.
5. modified material according to claim 1, which is characterized in that the polyethylene terephthalate degree of polymerization is
900-1100。
6. modified material according to claim 5, which is characterized in that the polyethylene terephthalate degree of polymerization is
1000。
7. a kind of preparation method of the modified material as described in claim any one of 1-6, which is characterized in that 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）Nano barium sulfate after cladding and polyethylene terephthalate are subjected to compound place in the electric field after mixing
Reason, obtains mixture；（4）Mixture and butadiene rubber, crosslinking agent, barium stearate are being subjected to combined processing after mixing,
Obtain polyethylene terephthalate modified material.
8. preparation method according to claim 7, which is characterized in that step（3）Middle electric field strength is 1.5-3.0kv/m.
9. preparation method according to claim 8, which is characterized in that step（3）Middle electric field strength is 2.0-2.5kv/m.
10. preparation method according to claim 7, which is characterized 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116622198A (en) * | 2023-06-07 | 2023-08-22 | 深圳市高科塑化有限公司 | Flexible impact-resistant engineering material and preparation method thereof |
| CN117186597A (en) * | 2023-09-13 | 2023-12-08 | 广州纽力斯新材料科技有限公司 | Environment-friendly type barrier film packaging material |
-
2017
- 2017-12-05 CN CN201711270615.6A patent/CN108047660A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116622198A (en) * | 2023-06-07 | 2023-08-22 | 深圳市高科塑化有限公司 | Flexible impact-resistant engineering material and preparation method thereof |
| CN116622198B (en) * | 2023-06-07 | 2024-08-16 | 深圳市高科塑化有限公司 | Flexible impact-resistant engineering material and preparation method thereof |
| CN117186597A (en) * | 2023-09-13 | 2023-12-08 | 广州纽力斯新材料科技有限公司 | Environment-friendly type barrier film packaging material |
| CN117186597B (en) * | 2023-09-13 | 2024-07-16 | 广州纽力斯新材料科技有限公司 | Environment-friendly type barrier film packaging material |
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