CN109135063A - A kind of polypropylene modified additive - Google Patents
A kind of polypropylene modified additive Download PDFInfo
- Publication number
- CN109135063A CN109135063A CN201811019653.9A CN201811019653A CN109135063A CN 109135063 A CN109135063 A CN 109135063A CN 201811019653 A CN201811019653 A CN 201811019653A CN 109135063 A CN109135063 A CN 109135063A
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- Prior art keywords
- modified additive
- polypropylene
- hours
- boron carbide
- carbide powder
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Abstract
The invention discloses a kind of polypropylene modified additives, are related to technical field of plastic, include the following steps and be made: (1) obtaining aliphatic APEO Composite Sub-micro boron carbide powder；(2) lipid reactant object is obtained；(3) modified additive is obtained；The present invention is by preparing polypropylene modified additive, the good lubricity of polypropylene plastics can be assigned, harmful friction is reduced and prevents polypropylene articles Interface Adhesion, the frictional force after melting between molecular resin can be reduced by addition modified additive of the present invention, the cohesive force between molten mass and process equipment can also be reduced, the flowing for promoting molten mass, to greatly improve polyacrylic processing performance.
Description
Technical field
The invention belongs to technical field of plastic, and in particular to a kind of polypropylene modified additive.
Background technique
Polypropylene is one of several plastics that usage amount is most wide in the world.Due to polypropylene itself have it is nontoxic, safe etc.
Feature, be widely used in the environment such as interior, car in, be the maximum plastics of dosage in automobile interior decoration.Even led in cutlery box
Domain is also developed rapidly, and mess-tin in 2015 is with polypropylene material Apparent con- sumption up to 150,000 t, it can be seen that, it is polyacrylic to apply model
It encloses to have obtained great extension.But existing polypropylene processing performance is general, melt index is lower, and impact strength is lower, nothing
Method meets the needs of certain occasions in market.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of polypropylene modified additive is provided.
The present invention is achieved by the following technical solutions:
A kind of polypropylene modified additive, includes the following steps and is made:
(1) submicron order boron carbide powder is mixed with metal nitrate saline solution by 1:22-24 mass ratio, then again at 68 DEG C
Lower immersion 25min, then the triethanolamine of submicron order boron carbide powder quality 5-6% is added, 35min is stirred with 550r/min revolving speed,
Then it is dry to constant weight to carry out rotary evaporation, obtains mixture, gained mixture is put into chemical vapor deposition stove, with indifferent gas
Body purges boiler tube, is subsequently passed hydrogen, increases temperature to 570 DEG C, then with the mixed gas of formaldehyde and hydrogen and replaces hydrogen, continues
Temperature is increased to 1080 DEG C, 2 hours is kept the temperature, then after cooled to room temperature, discharges, obtain reactant, by reactant
After mixing with aliphatic APEO by 15:1 mass ratio, 100 DEG C are heated to, is stirred 3 hours with 2000r/min revolving speed,
Then it is filtered, after drying to constant weight, then using deionized water cleaning, then carries out secondary drying, obtain aliphatic polyoxy
Vinethene Composite Sub-micro boron carbide powder；
(2) 2- monoglyceride is mixed with fatty acid vinyl ester by 1:3-5 molar ratio, is then added to 15 times of 2- monoglyceride quality
In organic solvent, the sulfuric acid solution that the mass fraction of 2- monoglyceride quality 0.5% is 75% is then added again, is heated to 98 DEG C, is protected
Temperature reaction 2 hours, then after cooled to room temperature, purifies reaction product, obtains lipid reactant object；
(3) stearic acid is added in reaction kettle, is then slowly heated to 80-83 DEG C in a nitrogen atmosphere again, then add tristearin
The catalyst of sour quality 0.35% stirs 40min with 500r/min revolving speed, then successively adds stearic acid quality 3.8-4.0% again
Aliphatic APEO Composite Sub-micro boron carbide powder and 5-5.5% above-mentioned lipid reactant object, continue stir 30min,
Then ethylenediamine is slowly added dropwise, is warming up to 128 DEG C, insulation reaction 2 hours, is then slowly warming up to 158 DEG C again, is kept for 5 hours,
Reaction is terminated when acid value is less than 9.5 mgKOH/g, then carries out rotary evaporation drying to constant weight to get the modified additive；
It is 1:2 that the stearic acid, which mixes molar ratio with ethylenediamine,.
Further, step (1) the submicron order boron carbide powder granularity is 0.22 μm.
Further, metal nitrate saline solution described in step (1) is the zinc nitrate solution that mass fraction is 5.8%.
Further, 1:3 is pressed under formaldehyde and hydrogen normal temperature and pressure in the mixed gas of formaldehyde and hydrogen described in step (1)
Volume ratio mixing.
Further, step (2) organic solvent is acetone.
Further, step (3) catalyst is phosphoric acid.
Further, the polypropylene modified additive is in use, when with acrylic resin hybrid process, by 100 weight
Part acrylic resin adds the part by weight modified auxiliary agent of 3.2-3.6.
The utility model has the advantages that the present invention by preparing polypropylene modified additive, can assign polypropylene plastics good lubrication
Property, reduce it is harmful rub and prevent polypropylene articles Interface Adhesion, after melting being reduced by adding modified additive of the present invention
Frictional force between molecular resin, additionally it is possible to the cohesive force between molten mass and process equipment is reduced, the flowing of molten mass is promoted,
To greatly improve polyacrylic processing performance, while to the surface light for improving device efficiency and yield rate, enhanced article
Damp degree plays extraordinary effect；Modified additive of the present invention is added to when being processed in acrylic resin, in heat and shearing
Under power effect, this hair is bought on the interface which modified additive is gradually repelled between acrylic resin and metal-working plant,
Improve outer lubricity, promote the flow rate of melt, so as to improve sample processing performance, when reducing material molding with set
Friction between standby is conducive to the surface gloss for improving polypropylene material, while can also preferably improve polypropylene plastics
Impact strength.
Specific embodiment
Embodiment 1
A kind of polypropylene modified additive, includes the following steps and is made:
(1) submicron order boron carbide powder is mixed with metal nitrate saline solution by 1:22 mass ratio, then again at 68 DEG C
25min is impregnated, then adds the triethanolamine of submicron order boron carbide powder quality 5%, 35min is stirred with 550r/min revolving speed, then
It is dry to constant weight to carry out rotary evaporation, obtains mixture, gained mixture is put into chemical vapor deposition stove, with inert blowing gas
Boiler tube is swept, hydrogen is subsequently passed, temperature is increased to 570 DEG C, then with the mixed gas of formaldehyde and hydrogen and replaces hydrogen, continue to increase
Temperature keeps the temperature 2 hours, then after cooled to room temperature, discharges, obtain reactant, by reactant and rouge to 1080 DEG C
After fat race polyoxyethylene ether is by the mixing of 15:1 mass ratio, 100 DEG C are heated to, with 2000r/min revolving speed stirring 3 hours, then
It is filtered, after drying to constant weight, then using deionized water cleaning, then carries out secondary drying, obtain aliphatic poly ethylene oxide
Ether Composite Sub-micro boron carbide powder；
(2) 2- monoglyceride is mixed with fatty acid vinyl ester by 1:3 molar ratio, is then added to having for 15 times of 2- monoglyceride quality
In solvent, the sulfuric acid solution that the mass fraction of 2- monoglyceride quality 0.5% is 75% is then added again, is heated to 98 DEG C, heat preservation
Reaction 2 hours, then after cooled to room temperature, purifies reaction product, obtains lipid reactant object；
(3) stearic acid is added in reaction kettle, is then slowly heated to 80 DEG C in a nitrogen atmosphere again, then add stearic acid matter
The catalyst of amount 0.35% stirs 40min with 500r/min revolving speed, then successively adds the aliphatic of stearic acid quality 3.8% again
Polyoxyethylene ether Composite Sub-micro boron carbide powder and 5% above-mentioned lipid reactant object, continue stir 30min, be then slowly added dropwise
Ethylenediamine is warming up to 128 DEG C, insulation reaction 2 hours, is then slowly warming up to 158 DEG C again, is kept for 5 hours, be less than to acid value
Reaction is terminated when 9.5 mgKOH/g, then carries out rotary evaporation drying to constant weight to get the modified additive；The stearic acid
It is 1:2 that molar ratio is mixed with ethylenediamine.
Further, step (1) the submicron order boron carbide powder granularity is 0.22 μm.
Further, metal nitrate saline solution described in step (1) is the zinc nitrate solution that mass fraction is 5.8%.
Further, 1:3 is pressed under formaldehyde and hydrogen normal temperature and pressure in the mixed gas of formaldehyde and hydrogen described in step (1)
Volume ratio mixing.
Further, step (2) organic solvent is acetone.
Further, step (3) catalyst is phosphoric acid.
Further, the polypropylene modified additive is in use, when with acrylic resin hybrid process, by 100 weight
Part acrylic resin adds 3.2 part by weight modified auxiliary agents.
Embodiment 2
A kind of polypropylene modified additive, includes the following steps and is made:
(1) submicron order boron carbide powder is mixed with metal nitrate saline solution by 1:24 mass ratio, then again at 68 DEG C
25min is impregnated, then adds the triethanolamine of submicron order boron carbide powder quality 6%, 35min is stirred with 550r/min revolving speed, then
It is dry to constant weight to carry out rotary evaporation, obtains mixture, gained mixture is put into chemical vapor deposition stove, with inert blowing gas
Boiler tube is swept, hydrogen is subsequently passed, temperature is increased to 570 DEG C, then with the mixed gas of formaldehyde and hydrogen and replaces hydrogen, continue to increase
Temperature keeps the temperature 2 hours, then after cooled to room temperature, discharges, obtain reactant, by reactant and rouge to 1080 DEG C
After fat race polyoxyethylene ether is by the mixing of 15:1 mass ratio, 100 DEG C are heated to, with 2000r/min revolving speed stirring 3 hours, then
It is filtered, after drying to constant weight, then using deionized water cleaning, then carries out secondary drying, obtain aliphatic poly ethylene oxide
Ether Composite Sub-micro boron carbide powder；
(2) 2- monoglyceride is mixed with fatty acid vinyl ester by 1:3-5 molar ratio, is then added to 15 times of 2- monoglyceride quality
In organic solvent, the sulfuric acid solution that the mass fraction of 2- monoglyceride quality 0.5% is 75% is then added again, is heated to 98 DEG C, is protected
Temperature reaction 2 hours, then after cooled to room temperature, purifies reaction product, obtains lipid reactant object；
(3) stearic acid is added in reaction kettle, is then slowly heated to 80-83 DEG C in a nitrogen atmosphere again, then add tristearin
The catalyst of sour quality 0.35% stirs 40min with 500r/min revolving speed, then successively adds the rouge of stearic acid quality 4.0% again
Fat race polyoxyethylene ether Composite Sub-micro boron carbide powder and 5.5% above-mentioned lipid reactant object, continue stir 30min, then delay
It is slow that ethylenediamine is added dropwise, 128 DEG C are warming up to, insulation reaction 2 hours, 158 DEG C is then slowly warming up to again, is kept for 5 hours, to acid value
Reaction is terminated when less than 9.5 mgKOH/g, then carries out rotary evaporation drying to constant weight to get the modified additive；It is described hard
It is 1:2 that resin acid, which mixes molar ratio with ethylenediamine,.
Further, step (1) the submicron order boron carbide powder granularity is 0.22 μm.
Further, metal nitrate saline solution described in step (1) is the zinc nitrate solution that mass fraction is 5.8%.
Further, 1:3 is pressed under formaldehyde and hydrogen normal temperature and pressure in the mixed gas of formaldehyde and hydrogen described in step (1)
Volume ratio mixing.
Further, step (2) organic solvent is acetone.
Further, step (3) catalyst is phosphoric acid.
Further, the polypropylene modified additive is in use, when with acrylic resin hybrid process, by 100 weight
Part acrylic resin adds 3.6 part by weight modified auxiliary agents.
Embodiment 3
A kind of polypropylene modified additive, includes the following steps and is made:
(1) submicron order boron carbide powder is mixed with metal nitrate saline solution by 1:23 mass ratio, then again at 68 DEG C
25min is impregnated, then adds the triethanolamine of submicron order boron carbide powder quality 5.5%, 35min is stirred with 550r/min revolving speed, so
It is dry to constant weight that rotary evaporation is carried out afterwards, is obtained mixture, gained mixture is put into chemical vapor deposition stove, with inert gas
Boiler tube is purged, hydrogen is subsequently passed, temperature is increased to 570 DEG C, then with the mixed gas of formaldehyde and hydrogen and replaces hydrogen, after of continuing rising
High-temperature to 1080 DEG C, keep the temperature 2 hours, then after cooled to room temperature, discharge, obtain reactant, by reactant with
After aliphatic APEO is by the mixing of 15:1 mass ratio, 100 DEG C are heated to, with 2000r/min revolving speed stirring 3 hours, so
After be filtered, after drying to constant weight, then using deionized water clean, then carry out secondary drying, obtain aliphatic polyoxy second
Alkene ether Composite Sub-micro boron carbide powder；
(2) 2- monoglyceride is mixed with fatty acid vinyl ester by 1:4 molar ratio, is then added to having for 15 times of 2- monoglyceride quality
In solvent, the sulfuric acid solution that the mass fraction of 2- monoglyceride quality 0.5% is 75% is then added again, is heated to 98 DEG C, heat preservation
Reaction 2 hours, then after cooled to room temperature, purifies reaction product, obtains lipid reactant object；
(3) stearic acid is added in reaction kettle, is then slowly heated to 81 DEG C in a nitrogen atmosphere again, then add stearic acid matter
The catalyst of amount 0.35% stirs 40min with 500r/min revolving speed, then successively adds the aliphatic of stearic acid quality 3.9% again
Polyoxyethylene ether Composite Sub-micro boron carbide powder and 5.2% above-mentioned lipid reactant object, continue stir 30min, then slowly drop
Add ethylenediamine, is warming up to 128 DEG C, insulation reaction 2 hours, is then slowly warming up to 158 DEG C again, is kept for 5 hours, be less than to acid value
Reaction is terminated when 9.5 mgKOH/g, then carries out rotary evaporation drying to constant weight to get the modified additive；The stearic acid
It is 1:2 that molar ratio is mixed with ethylenediamine.
Further, step (1) the submicron order boron carbide powder granularity is 0.22 μm.
Further, metal nitrate saline solution described in step (1) is the zinc nitrate solution that mass fraction is 5.8%.
Further, 1:3 is pressed under formaldehyde and hydrogen normal temperature and pressure in the mixed gas of formaldehyde and hydrogen described in step (1)
Volume ratio mixing.
Further, step (2) organic solvent is acetone.
Further, step (3) catalyst is phosphoric acid.
Further, the polypropylene modified additive is in use, when with acrylic resin hybrid process, by 100 weight
Part acrylic resin adds 3.4 part by weight modified auxiliary agents.
Comparative example 1: it is only that in modified additive preparation with the difference of embodiment 1 and does not add the compound Asia of aliphatic APEO
Micron order boron carbide powder.
Comparative example 2: the lipid reactant for being only that and not adding step (2) preparation in modified additive preparation is distinguished with embodiment 1
Object.
Control group: the virgin pp of modified additive is not added.
Fusion index instrument: HT-9431, Hongda Instruments Co., Ltd., cantilever shock machine: XJV-22, Chengde experimental machine
Co., Ltd is added in acrylic resin embodiment and comparative example modifying agent by 3.2:100 weight part ratio；Using phase
It is detected with melt index when technique processing, impact strength detection is carried out to manufactured same sample item；
Table 1
| Melt index g/10min | Impact strength kJ/m2 | |
| Embodiment mean value | 4.65 | 7.12 |
| Comparative example 1 | 4.28 | 6.35 |
| Comparative example 2 | 3.63 | 6.91 |
| Control group | 2.46 | 5.83 |
Modified additive of the present invention can effectively improve the melt index and impact strength of Pp System as can be seen from Table 1.
Claims (7)
1. a kind of polypropylene modified additive, which is characterized in that include the following steps and be made:
(1) submicron order boron carbide powder is mixed with metal nitrate saline solution by 1:22-24 mass ratio, then again at 68 DEG C
Lower immersion 25min, then the triethanolamine of submicron order boron carbide powder quality 5-6% is added, 35min is stirred with 550r/min revolving speed,
Then it is dry to constant weight to carry out rotary evaporation, obtains mixture, gained mixture is put into chemical vapor deposition stove, with indifferent gas
Body purges boiler tube, is subsequently passed hydrogen, increases temperature to 570 DEG C, then with the mixed gas of formaldehyde and hydrogen and replaces hydrogen, continues
Temperature is increased to 1080 DEG C, 2 hours is kept the temperature, then after cooled to room temperature, discharges, obtain reactant, by reactant
After mixing with aliphatic APEO by 15:1 mass ratio, 100 DEG C are heated to, is stirred 3 hours with 2000r/min revolving speed,
Then it is filtered, after drying to constant weight, then using deionized water cleaning, then carries out secondary drying, obtain aliphatic polyoxy
Vinethene Composite Sub-micro boron carbide powder；
(2) 2- monoglyceride is mixed with fatty acid vinyl ester by 1:3-5 molar ratio, is then added to 15 times of 2- monoglyceride quality
In organic solvent, the sulfuric acid solution that the mass fraction of 2- monoglyceride quality 0.5% is 75% is then added again, is heated to 98 DEG C, is protected
Temperature reaction 2 hours, then after cooled to room temperature, purifies reaction product, obtains lipid reactant object；
(3) stearic acid is added in reaction kettle, is then slowly heated to 80-83 DEG C in a nitrogen atmosphere again, then add tristearin
The catalyst of sour quality 0.35% stirs 40min with 500r/min revolving speed, then successively adds stearic acid quality 3.8-4.0% again
Aliphatic APEO Composite Sub-micro boron carbide powder and 5-5.5% above-mentioned lipid reactant object, continue stir 30min,
Then ethylenediamine is slowly added dropwise, is warming up to 128 DEG C, insulation reaction 2 hours, is then slowly warming up to 158 DEG C again, is kept for 5 hours,
Reaction is terminated when acid value is less than 9.5 mgKOH/g, then carries out rotary evaporation drying to constant weight to get the modified additive；
It is 1:2 that the stearic acid, which mixes molar ratio with ethylenediamine,.
2. a kind of polypropylene modified additive as described in claim 1, which is characterized in that step (1) the submicron order carbon
Changing boron Powder Particle Size is 0.22 μm.
3. a kind of polypropylene modified additive as described in claim 1, which is characterized in that metal nitrate described in step (1)
Saline solution is the zinc nitrate solution that mass fraction is 5.8%.
4. a kind of polypropylene modified additive as described in claim 1, which is characterized in that formaldehyde and hydrogen described in step (1)
Formaldehyde is mixed under hydrogen normal temperature and pressure by 1:3 volume ratio in the mixed gas of gas.
5. a kind of polypropylene modified additive as described in claim 1, which is characterized in that step (2) described organic solvent is
Acetone.
6. a kind of polypropylene modified additive as described in claim 1, which is characterized in that step (3) catalyst is phosphorus
Acid.
7. a kind of polypropylene modified additive as described in claim 1, which is characterized in that the polypropylene is made with modified additive
Used time when with acrylic resin hybrid process, adds the part by weight modified auxiliary agent of 3.2-3.6 by 100 parts by weight of polypropylene resins.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811019653.9A CN109135063A (en) | 2018-09-03 | 2018-09-03 | A kind of polypropylene modified additive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811019653.9A CN109135063A (en) | 2018-09-03 | 2018-09-03 | A kind of polypropylene modified additive |
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| Publication Number | Publication Date |
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| CN109135063A true CN109135063A (en) | 2019-01-04 |
Family
ID=64826364
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| CN201811019653.9A Pending CN109135063A (en) | 2018-09-03 | 2018-09-03 | A kind of polypropylene modified additive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210184A (en) * | 2020-10-13 | 2021-01-12 | 浦江羽洋塑胶有限公司 | Preparation method of high-resilience material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585977A (en) * | 2009-06-12 | 2009-11-25 | 武汉理工大学 | Preparation method of polypropylene reinforced plasticized modifier |
| CN101831108A (en) * | 2010-04-13 | 2010-09-15 | 四川大学 | Composite modified polypropylene material and preparation method thereof |
| CN106674736A (en) * | 2016-12-16 | 2017-05-17 | 华南协同创新研究院 | Polypropylene/boron carbide composite material for 3D (three-dimensional) printing and preparation method |
| CN107880384A (en) * | 2017-11-07 | 2018-04-06 | 日丰企业集团有限公司 | A kind of activeness and quietness polypropylene material and preparation method thereof |
-
2018
- 2018-09-03 CN CN201811019653.9A patent/CN109135063A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585977A (en) * | 2009-06-12 | 2009-11-25 | 武汉理工大学 | Preparation method of polypropylene reinforced plasticized modifier |
| CN101831108A (en) * | 2010-04-13 | 2010-09-15 | 四川大学 | Composite modified polypropylene material and preparation method thereof |
| CN106674736A (en) * | 2016-12-16 | 2017-05-17 | 华南协同创新研究院 | Polypropylene/boron carbide composite material for 3D (three-dimensional) printing and preparation method |
| CN107880384A (en) * | 2017-11-07 | 2018-04-06 | 日丰企业集团有限公司 | A kind of activeness and quietness polypropylene material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112210184A (en) * | 2020-10-13 | 2021-01-12 | 浦江羽洋塑胶有限公司 | Preparation method of high-resilience material |
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Application publication date: 20190104 |