CN108559259A - A kind of waste rubber powder doping nylon plastic material and preparation method thereof - Google Patents
A kind of waste rubber powder doping nylon plastic material and preparation method thereof Download PDFInfo
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- CN108559259A CN108559259A CN201810491891.3A CN201810491891A CN108559259A CN 108559259 A CN108559259 A CN 108559259A CN 201810491891 A CN201810491891 A CN 201810491891A CN 108559259 A CN108559259 A CN 108559259A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08K2003/3009—Sulfides
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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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
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Abstract
The invention discloses a kind of waste rubber powders to adulterate nylon plastic material, it is made of the raw material of following weight parts：Modified rubber powder 10 14, caprolactam 140 150,1-hydroxy ethylidene-1,1-diphosphonic acid 23, dibenzoyl peroxide 34,1,2 methylimidazoles 0.1 0.2, ethylene bis stearamide 0.7 1, calcium ricinoleate 12, bentonite 13 20, stannous sulfide 0.1 0.2.The finished-product material mechanical stability of the present invention is good, is adulterated by waste rubber powder, can not only further increase hydrophobicity and mechanical property, and can make full use of waste material, reduces production cost.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of waste rubber powder doping nylon plastic material and its preparation side
Method.
Background technology
Nylon has very strong vitality, it is modified to essentially consist in it as maximum most important kind in engineering plastics
Realize high performance, the followed by requirement high performance to product of the industries itself such as automobile, electric appliance, communication, electronics, machinery increasingly
Strongly, the rapid development of related industry promotes the process of engineering plastics high performance, and modification of nylon future developing trend is such as
Under：1. the market demand of high intensity high rigidity nylon is increasing, new reinforcing material such as inorganic crystal whisker enhancing, carbon fiber increase
Strong PA is mainly used for automotive engine component, mechanical part and air equipment component by as important kind.2. nylon
The mainstream that alloying will develop as modified engineered plastic.Nylon alloy is the high performance important channel of realization nylon, and
Manufacture nylon, nylon PP Pipe Compound, the main means for improving properties of nylons.By blending other high polymers, to improve the suction of nylon
It is aqueous, improve dimensional stability and black brittleness, the heat resistance and wearability of product.To be applicable in what car type difference required
Purposes.3. the manufacturing technology of nano-nylon will be rapidly developed with application.The advantages of nano-nylon, is its hot property, mechanics
Performance, anti-flammability, barrier property are higher than pure nylon, and manufacturing cost is suitable with common nylon.Thus, there is prodigious competitiveness.
4. for electronics, electrical, the fire-retardant nylon of electric appliance is growing day by day, greenization fire-retardant nylon is increasingly paid attention to by market.⑤
Antistatic, electroconductive nylon and magnetic nylon will be as the preferred materials of electronic equipment, mining machinery, textile machine.6. processing
The research and application of auxiliary agent will push the functionalization of modification of nylon, the process of high performance.7. polytechnic application, product
Fining be push its industry development power；
In recent years, with state's manufacturing industry high speed development at this stage, all trades and professions product up-gradation speed is further frequent, to product material
Performance more stringent requirements are proposed, therefore further promote the performance of nylon and to expand its use scope imperative.
Invention content
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of doping nylon modelings of waste rubber powder
Expect material and preparation method thereof.
To achieve the above object, the present invention uses following technical scheme：
A kind of waste rubber powder doping nylon plastic material, it is made of the raw material of following weight parts：
Modified rubber powder 10-14, caprolactam 140-150,1-hydroxy ethylidene-1,1-diphosphonic acid 2-3, dibenzoyl peroxide 3-4,1,2-
Methylimidazole 0.1-0.2, ethylene bis stearamide 0.7-1, calcium ricinoleate 1-2, bentonite 13-20, stannous sulfide 0.1-
0.2。
The modified rubber powder is made of the raw material of following weight parts：
Anti-aging agent CMA 0.1-0.2, waste rubber powder 17-20, dimethylaminopropylamine 1-2, calcium phosphate 5-6, pentaerythrite 3-4,
Methyl pyrrolidone 12-20；
The preparation method of the modified rubber powder, includes the following steps：
（1）The calcium phosphate is added in the deionized water of 30-40 times of its weight, and pentaerythrite is added, and is increased temperature and is
50-60 DEG C, dimethylaminopropylamine is added, insulated and stirred 10-29 minutes obtains ammoniated solution；
（2）Anti-aging agent CMA is taken, is added in methyl pyrrolidone, is stirred evenly, alkanone solution is obtained；
（3）Above-mentioned waste rubber powder is taken, is added in alkanone solution, stirs evenly, it is 60-65 DEG C to increase temperature, insulated and stirred
It 30-40 minutes, is mixed with above-mentioned ammoniated solution, precipitation is washed in 1-2 hours ultrasonic, filtering, and air drying obtains modified rubber
Powder.
A kind of preparation method of waste rubber powder doping nylon plastic material, includes the following steps：
（1）Dibenzoyl peroxide is taken, is added in the isopropanol of 10-15 times of its weight, stirs evenly；
（2）Bentonite is taken, is calcined 1-2 hours at 700-750 DEG C, is cooled to room temperature, wears into fine powder, with 1-hydroxy ethylidene-1,1-diphosphonic acid
Mixing, is added in the deionized water of 10-14 times of mixture weight, insulated and stirred 30-40 minutes at 55-60 DEG C, obtains swelling
Native solution；
（3）Calcium ricinoleate is taken, is added in the absolute ethyl alcohol of 6-8 times of its weight, stirs evenly, triethylamine is added, ultrasonic 2-3 divides
Clock obtains alcohol dispersion liquid；
（4）Caprolactam is taken, is added in the deionized water of 26-30 times of its weight, stirs evenly, it is mixed with above-mentioned bentonite solution
It closes, is sent in reaction kettle, be passed through nitrogen, it is 70-75 DEG C to adjust temperature of reaction kettle, and the different of above-mentioned dibenzoyl peroxide is added
Propanol solution, insulated and stirred 4-5 hours, discharging obtain polyamide solution；
（5）Above-mentioned modified rubber powder is taken, is added in alcohol dispersion liquid, stirs evenly, is mixed with above-mentioned polyamide solution, temperature is increased
Degree is 70-75 DEG C, insulated and stirred 1-2 hours, and precipitation is washed in filtering, and air drying obtains rubber-modified polyamide；
（6）Above-mentioned rubber-modified polyamide is taken, is mixed with remaining each raw material, stirs evenly, be sent in extruder, melting is squeezed
Go out, it is cooling to adulterate nylon plastic material to get the waste rubber powder.
Advantages of the present invention：
The present invention uses dimethylaminopropylamine to handle calcium phosphate first, is blended with waste rubber powder, divides in methyl pyrrolidone
It dissipates, obtains amino modified rubber powder, use 1-hydroxy ethylidene-1,1-diphosphonic acid to handle bentonite later, with obtained bentonite dispersion liquid
Dispersibility of the bentonite between polymer is improved using caprolactam as monomer polymerization for solvent, it is later that this is bentonite modified
Polymer be blended with amino modified rubber powder, reacted as solvent using the alcoholic solution containing triethylamine, to further
Dispersion performance of the rubber powder between polymer is improved, finished-product material mechanical stability of the invention is good, passes through waste rubber powder
Doping, can not only further increase hydrophobicity and mechanical property, and can make full use of waste material, reduction is produced into
This.
Specific implementation mode
Embodiment 1
A kind of waste rubber powder doping nylon plastic material, it is made of the raw material of following weight parts：
Modified rubber powder 14, caprolactam 150,1-hydroxy ethylidene-1,1-diphosphonic acid 3, dibenzoyl peroxide 4, DMIZ 1,2 dimethylimidazole
0.2, ethylene bis stearamide 1, calcium ricinoleate 2, bentonite 20, stannous sulfide 0.2.
The modified rubber powder is made of the raw material of following weight parts：
Anti-aging agent CMA 0.2, waste rubber powder 20, dimethylaminopropylamine 2, calcium phosphate 6, pentaerythrite 4, methyl pyrrolidone
20；
The preparation method of the modified rubber powder, includes the following steps：
（1）The calcium phosphate is added in the deionized water of 40 times of its weight, and pentaerythrite is added, and raising temperature is 50-60
DEG C, dimethylaminopropylamine is added, insulated and stirred 29 minutes obtains ammoniated solution；
（2）Anti-aging agent CMA is taken, is added in methyl pyrrolidone, is stirred evenly, alkanone solution is obtained；
（3）Above-mentioned waste rubber powder is taken, is added in alkanone solution, stirs evenly, it is 65 DEG C to increase temperature, and insulated and stirred 40 is divided
Clock is mixed with above-mentioned ammoniated solution, ultrasound 2 hours, and precipitation is washed in filtering, and air drying obtains modified rubber powder.
A kind of preparation method of waste rubber powder doping nylon plastic material, includes the following steps：
（1）Dibenzoyl peroxide is taken, is added in the isopropanol of 15 times of its weight, stirs evenly；
（2）Bentonite is taken, is calcined 2 hours at 750 DEG C, is cooled to room temperature, wears into fine powder, mixed with 1-hydroxy ethylidene-1,1-diphosphonic acid,
It is added in the deionized water of 14 times of mixture weight, insulated and stirred 40 minutes, obtain bentonite solution at 60 DEG C；
（3）Calcium ricinoleate is taken, is added in the absolute ethyl alcohol of 8 times of its weight, stirs evenly, triethylamine is added, it is 3 minutes ultrasonic,
Obtain alcohol dispersion liquid；
（4）Caprolactam is taken, is added in the deionized water of 30 times of its weight, stirs evenly, mixed with above-mentioned bentonite solution,
It is sent in reaction kettle, is passed through nitrogen, it is 75 DEG C to adjust temperature of reaction kettle, and the isopropanol that above-mentioned dibenzoyl peroxide is added is molten
Liquid, insulated and stirred 5 hours, discharging obtain polyamide solution；
（5）Above-mentioned modified rubber powder is taken, is added in alcohol dispersion liquid, stirs evenly, is mixed with above-mentioned polyamide solution, temperature is increased
Degree is 75 DEG C, insulated and stirred 2 hours, and precipitation is washed in filtering, and air drying obtains rubber-modified polyamide；
（6）Above-mentioned rubber-modified polyamide is taken, is mixed with remaining each raw material, stirs evenly, be sent in extruder, melting is squeezed
Go out, it is cooling to adulterate nylon plastic material to get the waste rubber powder.
Embodiment 2
A kind of waste rubber powder doping nylon plastic material, it is made of the raw material of following weight parts：
Modified rubber powder 10, caprolactam 140,1-hydroxy ethylidene-1,1-diphosphonic acid 2, dibenzoyl peroxide 3, DMIZ 1,2 dimethylimidazole
0.1, ethylene bis stearamide 0.7, calcium ricinoleate 1, bentonite 13, stannous sulfide 0.1.
The modified rubber powder is made of the raw material of following weight parts：
Anti-aging agent CMA 0.1, waste rubber powder 17, dimethylaminopropylamine 1, calcium phosphate 5, pentaerythrite 3, methyl pyrrolidone
12；
The preparation method of the modified rubber powder, includes the following steps：
（1）The calcium phosphate is added in the deionized water of 30 times of its weight, and pentaerythrite is added, and it is 50 DEG C to increase temperature,
Dimethylaminopropylamine is added, insulated and stirred 10 minutes obtains ammoniated solution；
（2）Anti-aging agent CMA is taken, is added in methyl pyrrolidone, is stirred evenly, alkanone solution is obtained；
（3）Above-mentioned waste rubber powder is taken, is added in alkanone solution, stirs evenly, it is 60 DEG C to increase temperature, and insulated and stirred 30 is divided
Clock is mixed with above-mentioned ammoniated solution, ultrasound 1 hour, and precipitation is washed in filtering, and air drying obtains modified rubber powder.
A kind of preparation method of waste rubber powder doping nylon plastic material, includes the following steps：
（1）Dibenzoyl peroxide is taken, is added in the isopropanol of 10 times of its weight, stirs evenly；
（2）Bentonite is taken, is calcined 1 hour at 700 DEG C, is cooled to room temperature, wears into fine powder, mixed with 1-hydroxy ethylidene-1,1-diphosphonic acid,
It is added in the deionized water of 10 times of mixture weight, insulated and stirred 30-40 minutes at 55 DEG C, obtains bentonite solution；
（3）Calcium ricinoleate is taken, is added in the absolute ethyl alcohol of 6 times of its weight, stirs evenly, triethylamine is added, it is 2 minutes ultrasonic,
Obtain alcohol dispersion liquid；
（4）Caprolactam is taken, is added in the deionized water of 26 times of its weight, stirs evenly, mixed with above-mentioned bentonite solution,
It is sent in reaction kettle, is passed through nitrogen, it is 70 DEG C to adjust temperature of reaction kettle, and the isopropanol that above-mentioned dibenzoyl peroxide is added is molten
Liquid, insulated and stirred 4 hours, discharging obtain polyamide solution；
（5）Above-mentioned modified rubber powder is taken, is added in alcohol dispersion liquid, stirs evenly, is mixed with above-mentioned polyamide solution, temperature is increased
Degree is 70 DEG C, insulated and stirred 1 hour, and precipitation is washed in filtering, and air drying obtains rubber-modified polyamide；
（6）Above-mentioned rubber-modified polyamide is taken, is mixed with remaining each raw material, stirs evenly, be sent in extruder, melting is squeezed
Go out, it is cooling to adulterate nylon plastic material to get the waste rubber powder.
Performance test：
The performance test of conventional nylon material：
Tensile strength：14-18MPa；
The tensile strength of the waste rubber powder doping nylon plastic material of the embodiment of the present invention 1 is 25.3MPa；
The tensile strength of the waste rubber powder doping nylon plastic material of the embodiment of the present invention 2 is 26.0MPa；
The waste rubber powder doping nylon plastic material of the embodiment of the present invention 1 is placed in water, soak at room temperature 60 hours takes out dry
Dry, it is 0.07% to measure tensile strength reduced rate；
The waste rubber powder doping nylon plastic material of the embodiment of the present invention 2 is placed in water, soak at room temperature 60 hours takes out dry
Dry, it is 0.10% to measure tensile strength reduced rate；
Conventional nylon material is placed in water, soak at room temperature 60 hours, takes out drying, measure tensile strength reduced rate 3.22%.
Claims (3)
1. a kind of waste rubber powder adulterates nylon plastic material, which is characterized in that it is made of the raw material of following weight parts：
Modified rubber powder 10-14, caprolactam 140-150,1-hydroxy ethylidene-1,1-diphosphonic acid 2-3, dibenzoyl peroxide 3-4,1,2-
Methylimidazole 0.1-0.2, ethylene bis stearamide 0.7-1, calcium ricinoleate 1-2, bentonite 13-20, stannous sulfide 0.1-
0.2。
2. a kind of waste rubber powder according to claim 1 adulterates nylon plastic material, which is characterized in that the modification
Rubber powder is made of the raw material of following weight parts：
Anti-aging agent CMA 0.1-0.2, waste rubber powder 17-20, dimethylaminopropylamine 1-2, calcium phosphate 5-6, pentaerythrite 3-4,
Methyl pyrrolidone 12-20；
The preparation method of the modified rubber powder, includes the following steps：
（1）The calcium phosphate is added in the deionized water of 30-40 times of its weight, and pentaerythrite is added, and is increased temperature and is
50-60 DEG C, dimethylaminopropylamine is added, insulated and stirred 10-29 minutes obtains ammoniated solution；
（2）Anti-aging agent CMA is taken, is added in methyl pyrrolidone, is stirred evenly, alkanone solution is obtained；
（3）Above-mentioned waste rubber powder is taken, is added in alkanone solution, stirs evenly, it is 60-65 DEG C to increase temperature, insulated and stirred
It 30-40 minutes, is mixed with above-mentioned ammoniated solution, precipitation is washed in 1-2 hours ultrasonic, filtering, and air drying obtains modified rubber
Powder.
3. a kind of preparation method of the waste rubber powder doping nylon plastic material as described in any in 1-2 such as claim, special
Sign is, includes the following steps：
（1）Dibenzoyl peroxide is taken, is added in the isopropanol of 10-15 times of its weight, stirs evenly；
（2）Bentonite is taken, is calcined 1-2 hours at 700-750 DEG C, is cooled to room temperature, wears into fine powder, with 1-hydroxy ethylidene-1,1-diphosphonic acid
Mixing, is added in the deionized water of 10-14 times of mixture weight, insulated and stirred 30-40 minutes at 55-60 DEG C, obtains swelling
Native solution；
（3）Calcium ricinoleate is taken, is added in the absolute ethyl alcohol of 6-8 times of its weight, stirs evenly, triethylamine is added, ultrasonic 2-3 divides
Clock obtains alcohol dispersion liquid；
（4）Caprolactam is taken, is added in the deionized water of 26-30 times of its weight, stirs evenly, it is mixed with above-mentioned bentonite solution
It closes, is sent in reaction kettle, be passed through nitrogen, it is 70-75 DEG C to adjust temperature of reaction kettle, and the different of above-mentioned dibenzoyl peroxide is added
Propanol solution, insulated and stirred 4-5 hours, discharging obtain polyamide solution；
（5）Above-mentioned modified rubber powder is taken, is added in alcohol dispersion liquid, stirs evenly, is mixed with above-mentioned polyamide solution, temperature is increased
Degree is 70-75 DEG C, insulated and stirred 1-2 hours, and precipitation is washed in filtering, and air drying obtains rubber-modified polyamide；
（6）Above-mentioned rubber-modified polyamide is taken, is mixed with remaining each raw material, stirs evenly, be sent in extruder, melting is squeezed
Go out, it is cooling to adulterate nylon plastic material to get the waste rubber powder.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980181A (en) * | 2021-02-08 | 2021-06-18 | 唐嫣 | Resin-coated modified nylon material and preparation method thereof |
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| US5051469A (en) * | 1985-12-13 | 1991-09-24 | Monsanto Company | Rubber modified reaction molded nylon-6 block copolymers |
| EP0510383A2 (en) * | 1991-04-23 | 1992-10-28 | BASF Aktiengesellschaft | High impact resistant moulding masses |
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| CN105504373A (en) * | 2015-12-17 | 2016-04-20 | 合肥杰明新材料科技有限公司 | High-stability plastic material and preparation method thereof |
| CN106009653A (en) * | 2016-08-05 | 2016-10-12 | 中山市绿浪助剂有限公司 | Antibacterial nano-silica material and preparation method thereof |
| CN107841076A (en) * | 2017-12-06 | 2018-03-27 | 安徽鸿宾医药包装有限公司 | A kind of toughness tear-proof packaging film and preparation method thereof |
-
2018
- 2018-05-22 CN CN201810491891.3A patent/CN108559259A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5051469A (en) * | 1985-12-13 | 1991-09-24 | Monsanto Company | Rubber modified reaction molded nylon-6 block copolymers |
| EP0510383A2 (en) * | 1991-04-23 | 1992-10-28 | BASF Aktiengesellschaft | High impact resistant moulding masses |
| CN105038200A (en) * | 2015-05-14 | 2015-11-11 | 湖南工业大学 | Multiple-composite-toughened nylon-6 composite material, composite toughening agent and preparation method thereof |
| CN105131590A (en) * | 2015-09-21 | 2015-12-09 | 高瑞杰 | Weather-proof anti-ultraviolet nylon material and preparation method thereof |
| CN105504373A (en) * | 2015-12-17 | 2016-04-20 | 合肥杰明新材料科技有限公司 | High-stability plastic material and preparation method thereof |
| CN106009653A (en) * | 2016-08-05 | 2016-10-12 | 中山市绿浪助剂有限公司 | Antibacterial nano-silica material and preparation method thereof |
| CN107841076A (en) * | 2017-12-06 | 2018-03-27 | 安徽鸿宾医药包装有限公司 | A kind of toughness tear-proof packaging film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112980181A (en) * | 2021-02-08 | 2021-06-18 | 唐嫣 | Resin-coated modified nylon material and preparation method thereof |
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Application publication date: 20180921 |