CN109251537A - A kind of environment-friendlyplasticizer plasticizer - Google Patents
A kind of environment-friendlyplasticizer plasticizer Download PDFInfo
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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Abstract
The present invention relates to a kind of environment-friendlyplasticizer plasticizers, belong to plasticizer manufacturing field.The present invention is mixed with adipic acid and terephthalic acids, obtain polyester-type plasticized modifier, be conducive to material and keep mechanical strength and rigidity, absorb more impact energys, improve impact strength, tensile strength is also improved, and plasticized modifier is improved the flexibility, oil resistivity and heat resistance of material matrix；With wolframic acid, phosphoric acid etc. for raw material, the flexibility of product is further increased, while it is with preferable processing performance, with preferable surface hardness and wear-resisting property, a part of petroleum base plasticizer can be replaced, reduce the usage amount of petroleum product, achieve the purpose that environmental protection；Using graphene oxide as raw material, so that plasticizer limits migration of plasticizer in use, it is fixed in frame structure.The problem of it is poor that the present invention solves current environment-friendly plasticizer hardness, tensile strength, is easy migration.
Description
Technical field
The present invention relates to plasticizer manufacturing technology field, especially a kind of environment-friendlyplasticizer plasticizer.
Background technique
As rubber and filler, plasticizer is represent for tire (pneumatic tire, bicycle tyre, solid rubber
Tire) rubber composition in and industrial rubber articles (hose, driving belt, other belts, cloth inserted rubber printing plate, film, pad
Piece, air spring, air bag, automotive interior panel, synthetic leather) in another important class additive.A large amount of plasticizer
Sometimes it is added in rubber composition, in order to reduce the cost of mixture, improve the flow behavior of mixture (during processing
Save energy, avoid energy peak), improve filler dispersion, improve deep processing behavior and adherency and changes mixture at behavior
With the physical characteristic of the curing rubber from its production.Nearly all plasticizer used in rubber industry is based generally on stone
Oil.For environment reason, it is especially considering that the in short supply of the horizontal and current raw material of current contamination discharge, future is increased
For the production for moulding agent, petroleum is no longer a kind of acceptable starting material.Under the situation of petroleum resources worsening shortages, exploitation
A kind of green, environmental protection plasticizer becomes the hot spot of everybody concern.The environment-friendly plasticizer occurred currently on the market is in hardness, tension
Compare shortcoming in intensity, is not able to satisfy the demand of people.
Summary of the invention
The technical problems to be solved by the invention: it is poor for current environment-friendly plasticizer hardness, tensile strength, it is easy migration
Problem provides a kind of environment-friendlyplasticizer plasticizer.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of environment-friendly type toughener includes following component, 20 ~ 40 parts of plasticized modifiers, 30 ~ 50 parts of rubber sections according to the mass fraction
Divide substitute, 18 ~ 25 parts of fixed additives；
The preparation method of the plasticized modifier, includes the following steps:
(1) it takes adipic acid 10 ~ 15:8 in mass ratio ~ 10 that terephthalic acid (TPA) is added to be stirred, adds 3 ~ 5 times of adipic acid quality
1,4-butanediol, be stirred in 90 ~ 100 DEG C, obtain mixture, be warming up to 180 ~ 190 DEG C, take mixture in mass ratio 90 ~
Titanium ethylene glycolate is added in 120:1 ~ 3, is passed through nitrogen protection, is stirred, keeps the temperature, be cooled to room temperature, obtain cooled material；
(2) it takes cooled material 2 ~ 5:8 in mass ratio ~ 10 that polyethylene glycol-6000 is added, is stirred, vacuumizes quiet in 130 ~ 140 DEG C
1 ~ 3h is set, stirring mixture is obtained, takes stirring mixture 20 ~ 30:4 in mass ratio ~ 7 to be added end-capping living dose, is passed through nitrogen protection,
It is stirred, is cooled to room temperature to get plasticized modifier.
The condition for being stirred, keeping the temperature of cooled material in the step (1) are as follows: be warming up to 210 ~ 220 DEG C be stirred 1 ~
3h, then it is warming up to 220 ~ 230 DEG C of 10 ~ 12h of heat preservation.
End-capping living dose in the step (2) are as follows: take hexamethylene diisocyanate, diethylene glycol monobutyl ether in mass ratio
3 ~ 7:2 ~ 4 mixing to get.
The preparation method of the rubber part substitute, includes the following steps:
S1. it takes hydrogen peroxide that wolframic acid is added by 10 ~ 20:1 of quality ~ 3, is stirred 40 ~ 60min in 55 ~ 60 DEG C, filter, take filtrate
Deionized water is added in 3 ~ 5:4 in mass ratio ~ 6, and the phosphoric acid stirring that the mass fraction for adding filtrate quality 20 ~ 30% is 40% is mixed
It closes, mixture a must be stirred, take halogenated phosphates 2 ~ 4:10 in mass ratio ~ 20 that ethyl acetate is added, obtain mixed liquor, take
Stirring mixture a is added in mixed liquor 5 ~ 8:20 in mass ratio ~ 30, and 20 ~ 30min is stirred in 25 ~ 30 DEG C, stands 1 ~ 3h, takes
Precipitating is dry through distillation water washing, obtains dried object；
S2. it takes cashew nut shell oil 2 ~ 5:3 in mass ratio ~ 8 that pentaerythrite is added, the dried object of cashew nut shell oil quality 3 ~ 7% is added, rise
To 110 ~ 120 DEG C, the trimethylbenzene for adding cashew nut shell oil quality 2 ~ 5% is stirred temperature, obtains mixture, takes mixture by quality
Ethyl acetate is added than 2 ~ 7:10 ~ 15, the hydrogen peroxide for adding mixture quality 10 ~ 20% is stirred, and filters, filtrate is taken to pass through
Saturated sodium chloride solution washing, is evaporated under reduced pressure to get rubber part substitute.
That mixture a is stirred in the step S1 is stirred condition are as follows: is warming up to 50 ~ 60 DEG C and is stirred 5 ~ 10min.
The hydrogen peroxide of mixture quality 10 ~ 20% is added in the step S2 is stirred condition are as follows: stirs in 60 ~ 65 DEG C
Mix 1 ~ 3h of mixing.
The fixed additive the preparation method comprises the following steps:
It takes tetradecy lamine 1 ~ 4:10 in mass ratio ~ 20 that dehydrated alcohol is added, is stirred 200 ~ 30min, obtains mixed liquor a, take oxidation
Mixed liquor a is added in graphene 3 ~ 8:8 in mass ratio ~ 10, is warming up to 55 ~ 60 DEG C and is stirred 10 ~ 12h, filters, takes filter residue through nothing
Water-ethanol washing, rotary evaporation are dry to get fixed additive.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention is mixed with adipic acid and terephthalic acids, and 1,4-butanediol is added, and titanium ethylene glycolate catalysis is added, then pass through
Hexamethylene diisocyanate, diethylene glycol monobutyl ether are blocked, and polyester-type plasticized modifier is obtained, with certain knot
Crystalline substance is conducive to material and mechanical strength and rigidity, the ester group of introducing is kept to be formed containing rigid benzene ring structure in strand
Segmented copolymer will disperse in blend of materials in dispersion phase surface, it is disconnected in impact to increase phase interface effect power
Cause shear yielding deformation during splitting, when dispersion particle being promoted to remove in material matrix, absorbs more impact energys
Amount, improves impact strength, so that tensile strength is also improved, while being introduced into the ether in diethylene glycol monobutyl ether, makes
Plasticized modifier is obtained to be improved the flexibility, oil resistivity and heat resistance of material matrix；
(2) present invention is added hydrogen peroxide and phase transfer catalyst is prepared with wolframic acid, phosphoric acid etc. for raw material, in catalysis cashew nut shell
During oil carries out esterification with pentaerythrite, the introducing of the organic peracids such as no carboxylic acid, so that catalytic process is stable, is not easy
Explosion, catalytic process environmental protection, while the product epoxide number being catalyzed increases, and promotes epoxidation process, generate containing carbomethoxy and
The introducing of the difunctional compound of epoxy group, epoxy group can form more hydrogen bonds with the polar group on material molecule, shorten
The segment scale of polymer improves the locomitivity of molecule segment, increases free volume, generally increases macromolecular main chain shifting
Dynamic chance, in addition, it is with long alkyl chain structure, and has screen effect and lubricity to polymer macromolecule, it can be into one
Step improves the flexibility of product, while it is with preferable processing performance, has preferable surface hardness and wear-resisting property, can be with
Replace a part of petroleum base plasticizer, reduce the usage amount of petroleum product, achievees the purpose that environmental protection；
(3) tetradecy lamine is added using graphene oxide as raw material in the present invention, so that the epoxy group and amido on graphene oxide carry out
Ring-opening reaction generates amido bond, using the design feature of graphene itself, has unlimited two-dimensional structure, to environment-friendly plasticizer into
Row fixation in situ is fixed in frame structure so that plasticizer limits migration of plasticizer in use, while passing through ten
The covalent functionalization of tetramine is modified, and graphene oxide becomes hydrophobic oleophilic oil, gets a promotion with the contact performance of plasticizer, increases
Contact angle, can be such that the fixed function of graphene gives full play to.
Specific embodiment
End-capping living dose are as follows: take hexamethylene diisocyanate, diethylene glycol monobutyl ether 3 ~ 7:2 in mass ratio ~ 4 to mix,
To obtain the final product.
Plasticized modifier the preparation method comprises the following steps: (1) take adipic acid 10 ~ 15:8 in mass ratio ~ 10 be added terephthalic acid (TPA), stir
20 ~ 30min of mixing is mixed, 3 ~ 5 times of adipic acid quality of 1,4-butanediol is added, is stirred 30 ~ 50min in 90 ~ 100 DEG C,
Mixture is obtained, is warming up to 180 ~ 190 DEG C, takes mixture 90 ~ 120:1 in mass ratio ~ 3 that titanium ethylene glycolate is added, is passed through nitrogen protection,
It is warming up to 210 ~ 220 DEG C and is stirred 1 ~ 3h, then be warming up to 220 ~ 230 DEG C of 10 ~ 12h of heat preservation, be cooled to room temperature, obtain cooled material；
(2) it takes cooled material 2 ~ 5:8 in mass ratio ~ 10 that polyethylene glycol-6000 is added, is stirred 30 ~ 60min in 130 ~ 140 DEG C,
1 ~ 3h of standing is vacuumized, stirring mixture is obtained, takes stirring mixture 20 ~ 30:4 in mass ratio ~ 7 to be added end-capping living dose, is passed through
Nitrogen protection is stirred 4 ~ 6h in 80 ~ 90 DEG C, is cooled to room temperature to get plasticized modifier.
Rubber part substitute the preparation method comprises the following steps:
S1. take the hydrogen peroxide that mass fraction is 30% that wolframic acid is added by 10 ~ 20:1 of quality ~ 3, it is stirred 40 in 55 ~ 60 DEG C ~
60min, filtering take filtrate 3 ~ 5:4 in mass ratio ~ 6 that deionized water is added, and the mass fraction for adding filtrate quality 20 ~ 30% is
40% phosphoric acid is warming up to 50 ~ 60 DEG C and is stirred 5 ~ 10min, must stir mixture a, take halogenated phosphates by quality
Ethyl acetate is added than 2 ~ 4:10 ~ 20, obtains mixed liquor, takes mixed liquor 5 ~ 8:20 in mass ratio ~ 30 that stirring mixture a is added, in
25 ~ 30 DEG C are stirred 20 ~ 30min, stand 1 ~ 3h, take precipitating dry through distillation water washing, obtain dried object；
S2. it takes cashew nut shell oil 2 ~ 5:3 in mass ratio ~ 8 that pentaerythrite is added, the dried object of cashew nut shell oil quality 3 ~ 7% is added, rise
Temperature adds the trimethylbenzene of cashew nut shell oil quality 2 ~ 5%, is stirred 1 ~ 3h, obtain mixture to 110 ~ 120 DEG C, take mixture by
Ethyl acetate is added in 2 ~ 7:10 of mass ratio ~ 15, adds the hydrogen peroxide that the mass fraction of mixture quality 10 ~ 20% is 30%, in
60 ~ 65 DEG C are stirred 1 ~ 3h, and filtering takes filtrate to wash through saturated sodium chloride solution, and vacuum distillation is to get rubber part substitution
Object.
Fixed additive the preparation method comprises the following steps:
It takes tetradecy lamine 1 ~ 4:10 in mass ratio ~ 20 that dehydrated alcohol is added, is stirred 200 ~ 300min, obtains mixed liquor a, take oxidation
Mixed liquor a is added in graphene 3 ~ 8:8 in mass ratio ~ 10, is warming up to 55 ~ 60 DEG C and is stirred 10 ~ 12h, filters, takes filter residue through nothing
Water-ethanol washing, rotary evaporation are dry to get fixed additive.
A kind of environment-friendly type toughener takes 20 ~ 40 parts of plasticized modifiers, 30 ~ 50 parts of rubber part substitutions according to the mass fraction
Object, 18 ~ 25 parts of fixed additives to get.
Embodiment 1
End-capping living dose are as follows: take hexamethylene diisocyanate, diethylene glycol monobutyl ether 3:2 in mass ratio mixing to get.
Plasticized modifier the preparation method comprises the following steps: (1) take adipic acid 10:8 in mass ratio be added terephthalic acid (TPA), be stirred
20min, adds 3 times of adipic acid quality of 1,4-butanediol, is stirred 30min in 90 DEG C, obtains mixture, be warming up to 180
DEG C, it takes mixture 90:1 in mass ratio that titanium ethylene glycolate is added, is passed through nitrogen protection, is warming up to 210 DEG C and is stirred 1h, then heat up
To 220 DEG C of heat preservation 10h, it is cooled to room temperature, obtains cooled material；
(2) it takes cooled material 2:8 in mass ratio that polyethylene glycol-6000 is added, is stirred 30min in 130 DEG C, vacuumizes standing
1h obtains stirring mixture, takes stirring mixture 20:4 to be in mass ratio added end-capping living dose, is passed through nitrogen protection, stirs in 80 DEG C
Mixing 4h is mixed, is cooled to room temperature to get plasticized modifier.
Rubber part substitute the preparation method comprises the following steps:
S1. it takes the hydrogen peroxide that mass fraction is 30% that wolframic acid is added by quality 10:1, is stirred 40min in 55 DEG C, filter, take
Deionized water is added in filtrate 3:4 in mass ratio, adds the phosphoric acid that the mass fraction of filtrate quality 20% is 40%, is warming up to 50 DEG C
It is stirred 5min, mixture a must be stirred, takes halogenated phosphates 2:10 in mass ratio that ethyl acetate is added, must mix
Liquid takes mixed liquor 5:20 in mass ratio that stirring mixture a is added, 20min is stirred in 25 DEG C, stand 1h, takes precipitating through steaming
Distilled water washs drying, obtains dried object；
S2. it takes cashew nut shell oil 2:3 in mass ratio that pentaerythrite is added, the dried object of cashew nut shell oil quality 3% is added, is warming up to 110
DEG C, the trimethylbenzene of cashew nut shell oil quality 2% is added, 1h is stirred, obtains mixture, mixture 2:10 in mass ratio is taken to be added
Ethyl acetate adds the hydrogen peroxide that the mass fraction of mixture quality 10% is 30%, is stirred 1h in 60 DEG C, filters, take
Filtrate is washed through saturated sodium chloride solution, is evaporated under reduced pressure to get rubber part substitute.
Fixed additive the preparation method comprises the following steps:
Take tetradecy lamine 1:10 in mass ratio be added dehydrated alcohol, be stirred 200min, obtain mixed liquor a, take graphene oxide by
Mixed liquor a is added in mass ratio 3:8, is warming up to 55 DEG C and is stirred 10h, filters, filter residue is taken to wash through dehydrated alcohol, and rotation is steamed
Hair, it is dry to get fixed additive.
A kind of environment-friendly type toughener takes 20 parts of plasticized modifiers, 30 parts of rubber part substitutes, 18 according to the mass fraction
Part fixed additive to get.
Embodiment 2
End-capping living dose are as follows: take hexamethylene diisocyanate, diethylene glycol monobutyl ether 7:4 in mass ratio mixing to get.
Plasticized modifier the preparation method comprises the following steps: (1) takes adipic acid 15:10 in mass ratio that terephthalic acid (TPA) is added, stirring is mixed
30min is closed, 5 times of adipic acid quality of 1,4-butanediol is added, is stirred 50min in 100 DEG C, obtains mixture, be warming up to
It 190 DEG C, takes mixture 120:3 in mass ratio that titanium ethylene glycolate is added, is passed through nitrogen protection, is warming up to 220 DEG C and is stirred 3h, then
230 DEG C of heat preservation 12h are warming up to, is cooled to room temperature, obtains cooled material；
(2) it takes cooled material 5:10 in mass ratio that polyethylene glycol-6000 is added, is stirred 60min in 140 DEG C, vacuumizes standing
3h obtains stirring mixture, takes stirring mixture 30:7 to be in mass ratio added end-capping living dose, is passed through nitrogen protection, stirs in 90 DEG C
Mixing 6h is mixed, is cooled to room temperature to get plasticized modifier.
Rubber part substitute the preparation method comprises the following steps:
S1. it takes the hydrogen peroxide that mass fraction is 30% that wolframic acid is added by quality 20:3, is stirred 60min in 60 DEG C, filter, take
Deionized water is added in filtrate 5:6 in mass ratio, adds the phosphoric acid that the mass fraction of filtrate quality 30% is 40%, is warming up to 60 DEG C
It is stirred 10min, mixture a must be stirred, takes halogenated phosphates 4:20 in mass ratio that ethyl acetate is added, must mix
Liquid takes mixed liquor 8:30 in mass ratio that stirring mixture a is added, 30min is stirred in 30 DEG C, stand 3h, takes precipitating through steaming
Distilled water washs drying, obtains dried object；
S2. it takes cashew nut shell oil 5:8 in mass ratio that pentaerythrite is added, the dried object of cashew nut shell oil quality 7% is added, is warming up to 120
DEG C, the trimethylbenzene of cashew nut shell oil quality 5% is added, 3h is stirred, obtains mixture, mixture 7:15 in mass ratio is taken to be added
Ethyl acetate adds the hydrogen peroxide that the mass fraction of mixture quality 20% is 30%, is stirred 3h in 65 DEG C, filters, take
Filtrate is washed through saturated sodium chloride solution, is evaporated under reduced pressure to get rubber part substitute.
Fixed additive the preparation method comprises the following steps:
Take tetradecy lamine 4:20 in mass ratio be added dehydrated alcohol, be stirred 300min, obtain mixed liquor a, take graphene oxide by
Mixed liquor a is added in mass ratio 8:10, is warming up to 60 DEG C and is stirred 12h, filters, filter residue is taken to wash through dehydrated alcohol, and rotation is steamed
Hair, it is dry to get fixed additive.
A kind of environment-friendly type toughener takes 40 parts of plasticized modifiers, 50 parts of rubber part substitutes, 25 according to the mass fraction
Part fixed additive to get.
Embodiment 3
End-capping living dose are as follows: take hexamethylene diisocyanate, diethylene glycol monobutyl ether 4:3 in mass ratio mixing to get.
Plasticized modifier the preparation method comprises the following steps: (1) take adipic acid 12:9 in mass ratio be added terephthalic acid (TPA), be stirred
25min, adds 4 times of adipic acid quality of 1,4-butanediol, is stirred 40min in 95 DEG C, obtains mixture, be warming up to 185
DEG C, it takes mixture 100:2 in mass ratio that titanium ethylene glycolate is added, is passed through nitrogen protection, is warming up to 215 DEG C and is stirred 2h, then rise
Temperature is cooled to room temperature to 225 DEG C of heat preservation 11h, obtains cooled material；
(2) it takes cooled material 3:9 in mass ratio that polyethylene glycol-6000 is added, is stirred 50min in 135 DEG C, vacuumizes standing
2h obtains stirring mixture, takes stirring mixture 25:6 to be in mass ratio added end-capping living dose, is passed through nitrogen protection, stirs in 85 DEG C
Mixing 5h is mixed, is cooled to room temperature to get plasticized modifier.
Rubber part substitute the preparation method comprises the following steps:
S1. it takes the hydrogen peroxide that mass fraction is 30% that wolframic acid is added by quality 15:2, is stirred 50min in 57 DEG C, filter, take
Deionized water is added in filtrate 4:5 in mass ratio, adds the phosphoric acid that the mass fraction of filtrate quality 25% is 40%, is warming up to 55 DEG C
It is stirred 7min, mixture a must be stirred, takes halogenated phosphates 3:15 in mass ratio that ethyl acetate is added, must mix
Liquid takes mixed liquor 7:25 in mass ratio that stirring mixture a is added, 25min is stirred in 27 DEG C, stand 2h, takes precipitating through steaming
Distilled water washs drying, obtains dried object；
S2. it takes cashew nut shell oil 3:5 in mass ratio that pentaerythrite is added, the dried object of cashew nut shell oil quality 4% is added, is warming up to 115
DEG C, the trimethylbenzene of cashew nut shell oil quality 3% is added, 2h is stirred, obtains mixture, mixture 5:12 in mass ratio is taken to be added
Ethyl acetate adds the hydrogen peroxide that the mass fraction of mixture quality 15% is 30%, is stirred 2h in 63 DEG C, filters, take
Filtrate is washed through saturated sodium chloride solution, is evaporated under reduced pressure to get rubber part substitute.
Fixed additive the preparation method comprises the following steps:
Take tetradecy lamine 3:16 in mass ratio be added dehydrated alcohol, be stirred 250min, obtain mixed liquor a, take graphene oxide by
Mixed liquor a is added in mass ratio 5:9, is warming up to 57 DEG C and is stirred 11h, filters, filter residue is taken to wash through dehydrated alcohol, and rotation is steamed
Hair, it is dry to get fixed additive.
A kind of environment-friendly type toughener takes 30 parts of plasticized modifiers, 40 parts of rubber part substitutes, 20 according to the mass fraction
Part fixed additive to get.
Comparative example: the environment-friendly plasticizer of company of Luoyang City production.
The environment-friendly plasticizer piller that above-described embodiment and comparative example are obtained produces sample appropriate by injecting molding
Product have machinery, shape and size characteristic required by relevant criterion.Detect the mechanical property below the sample: according to
The tensile strength of ASTM standard D638；According to the elasticity modulus of ASTM standard D790；According to the Rockwell of ASTM standard D785
(Rockwell) hardness；According to Charpy (Charpy) impact strength of iso standard 179, the mechanical performance that these samples are carried out
The result of test is shown in table 1 below.
Table 1:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Tensile strength/Mpa | 58 | 49 | 51 | 45 | 33 | 34 | 27 |
| Elasticity modulus/Mpa | 2698 | 1891 | 1789 | 1695 | 1578 | 1563 | 1469 |
| Hardness/R | 118 | 117 | 114 | 105 | 102 | 100 | 96 |
| Impact strength/KJ/m2 | 172 | 158 | 139 | 116 | 102 | 92 | 65 |
In conclusion as shown in Table 1, the environment-friendly plasticizer of environment-friendly plasticizer prepared by the present invention and comparative example is than hardness, tension
Intensity is good, it is not easy to migrate, be worth advocating using energetically.
Claims (7)
1. a kind of environment-friendly type toughener, which is characterized in that according to the mass fraction include following component, 20 ~ 40 parts of plasticized modifiers,
30 ~ 50 parts of rubber part substitutes, 18 ~ 25 parts of fixed additives；
The preparation method of the plasticized modifier, includes the following steps:
(1) it takes adipic acid 10 ~ 15:8 in mass ratio ~ 10 that terephthalic acid (TPA) is added to be stirred, adds 3 ~ 5 times of adipic acid quality
1,4-butanediol, be stirred in 90 ~ 100 DEG C, obtain mixture, be warming up to 180 ~ 190 DEG C, take mixture in mass ratio 90 ~
Titanium ethylene glycolate is added in 120:1 ~ 3, is passed through nitrogen protection, is stirred, keeps the temperature, be cooled to room temperature, obtain cooled material；
(2) it takes cooled material 2 ~ 5:8 in mass ratio ~ 10 that polyethylene glycol-6000 is added, is stirred, vacuumizes quiet in 130 ~ 140 DEG C
1 ~ 3h is set, stirring mixture is obtained, takes stirring mixture 20 ~ 30:4 in mass ratio ~ 7 to be added end-capping living dose, is passed through nitrogen protection,
It is stirred, is cooled to room temperature to get plasticized modifier.
2. environment-friendly type toughener according to claim 1, which is characterized in that the stirring of cooled material is mixed in the step (1)
It closes, the condition of heat preservation are as follows: be warming up to 210 ~ 220 DEG C and be stirred 1 ~ 3h, then be warming up to 220 ~ 230 DEG C of 10 ~ 12h of heat preservation.
3. environment-friendly type toughener according to claim 1, which is characterized in that end-capping living dose in the step (2) are as follows: take
Hexamethylene diisocyanate, diethylene glycol monobutyl ether 3 ~ 7:2 in mass ratio ~ 4 mixing to get.
4. environment-friendly type toughener according to claim 1, which is characterized in that the preparation side of the rubber part substitute
Method includes the following steps:
S1. it takes hydrogen peroxide that wolframic acid is added by 10 ~ 20:1 of quality ~ 3, is stirred 40 ~ 60min in 55 ~ 60 DEG C, filter, take filtrate
Deionized water is added in 3 ~ 5:4 in mass ratio ~ 6, and the phosphoric acid stirring that the mass fraction for adding filtrate quality 20 ~ 30% is 40% is mixed
It closes, mixture a must be stirred, take halogenated phosphates 2 ~ 4:10 in mass ratio ~ 20 that ethyl acetate is added, obtain mixed liquor, take
Stirring mixture a is added in mixed liquor 5 ~ 8:20 in mass ratio ~ 30, and 20 ~ 30min is stirred in 25 ~ 30 DEG C, stands 1 ~ 3h, takes
Precipitating is dry through distillation water washing, obtains dried object；
S2. it takes cashew nut shell oil 2 ~ 5:3 in mass ratio ~ 8 that pentaerythrite is added, the dried object of cashew nut shell oil quality 3 ~ 7% is added, rise
To 110 ~ 120 DEG C, the trimethylbenzene for adding cashew nut shell oil quality 2 ~ 5% is stirred temperature, obtains mixture, takes mixture by quality
Ethyl acetate is added than 2 ~ 7:10 ~ 15, the hydrogen peroxide for adding mixture quality 10 ~ 20% is stirred, and filters, filtrate is taken to pass through
Saturated sodium chloride solution washing, is evaporated under reduced pressure to get rubber part substitute.
5. environment-friendly type toughener according to claim 1, which is characterized in that stir stirring for mixture a in the step S1
Mix mixing condition are as follows: be warming up to 50 ~ 60 DEG C and be stirred 5 ~ 10min.
6. environment-friendly type toughener according to claim 1, which is characterized in that mixture quality 10 is added in the step S2
~ 20% hydrogen peroxide is stirred condition are as follows: is stirred 1 ~ 3h in 60 ~ 65 DEG C.
7. environment-friendly type toughener according to claim 1, which is characterized in that the fixed additive the preparation method comprises the following steps:
It takes tetradecy lamine 1 ~ 4:10 in mass ratio ~ 20 that dehydrated alcohol is added, is stirred 200 ~ 30min, obtains mixed liquor a, take oxidation
Mixed liquor a is added in graphene 3 ~ 8:8 in mass ratio ~ 10, is warming up to 55 ~ 60 DEG C and is stirred 10 ~ 12h, filters, takes filter residue through nothing
Water-ethanol washing, rotary evaporation are dry to get fixed additive.
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|---|---|---|---|---|
| CN114277611A (en) * | 2021-12-31 | 2022-04-05 | 佛山荷韵特种材料有限公司 | Special explosion-proof flower cover oil for ceramic stained paper, production process of special explosion-proof flower cover oil and ceramic stained paper |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140165A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Biodegradable copolyester and preparation method thereof |
| CN104130365A (en) * | 2014-07-22 | 2014-11-05 | 南京林业大学 | Linear polyurethane elastomer toughener toughening biopolyester PHA, and preparation method and application thereof |
| CN104926648A (en) * | 2015-06-06 | 2015-09-23 | 山东岩海建设资源有限公司 | Polyester plasticizer as well as preparation method and application thereof |
| CN107001749A (en) * | 2014-10-29 | 2017-08-01 | 瑞西纳特材料集团有限公司 | Polymeric plasticiser composition |
-
2018
- 2018-08-29 CN CN201810995489.9A patent/CN109251537A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140165A (en) * | 2010-02-03 | 2011-08-03 | 中国石油天然气股份有限公司 | Biodegradable copolyester and preparation method thereof |
| CN104130365A (en) * | 2014-07-22 | 2014-11-05 | 南京林业大学 | Linear polyurethane elastomer toughener toughening biopolyester PHA, and preparation method and application thereof |
| CN104130365B (en) * | 2014-07-22 | 2016-11-02 | 南京林业大学 | A kind of linear polyurethane elastic body toughening agent of toughness reinforcing Biopolvester PHA and its preparation method and application |
| CN107001749A (en) * | 2014-10-29 | 2017-08-01 | 瑞西纳特材料集团有限公司 | Polymeric plasticiser composition |
| CN104926648A (en) * | 2015-06-06 | 2015-09-23 | 山东岩海建设资源有限公司 | Polyester plasticizer as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘西文: "《塑料配混工（中、高级）培训教程》", 31 January 2017, 文化发展出版社 * |
| 陈洁: "生物基环氧类增塑剂的合成及性能研究", 《中国博士学位论文全文数据库工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114277611A (en) * | 2021-12-31 | 2022-04-05 | 佛山荷韵特种材料有限公司 | Special explosion-proof flower cover oil for ceramic stained paper, production process of special explosion-proof flower cover oil and ceramic stained paper |
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