CN102532660B - Solvent-resistant macromolecular blending material for injection molding - Google Patents
Solvent-resistant macromolecular blending material for injection molding Download PDFInfo
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- CN102532660B CN102532660B CN 201110437659 CN201110437659A CN102532660B CN 102532660 B CN102532660 B CN 102532660B CN 201110437659 CN201110437659 CN 201110437659 CN 201110437659 A CN201110437659 A CN 201110437659A CN 102532660 B CN102532660 B CN 102532660B
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000001746 injection moulding Methods 0.000 title claims abstract description 15
- 239000002904 solvent Substances 0.000 title abstract description 17
- 238000002156 mixing Methods 0.000 title abstract 3
- 239000004743 Polypropylene Substances 0.000 claims abstract description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 16
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 15
- -1 polypropylene Polymers 0.000 claims abstract description 12
- 238000012360 testing method Methods 0.000 claims description 17
- 239000012296 anti-solvent Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005453 pelletization Methods 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229920002292 Nylon 6 Polymers 0.000 abstract description 4
- 229920006124 polyolefin elastomer Polymers 0.000 abstract 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000035939 shock Effects 0.000 description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 6
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 241000863032 Trieres Species 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
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Abstract
The invention relates to a macromolecular material, in particular to a solvent-resistant macromolecular blending material for injection molding. A homopolymerized polypropylene (PP) with good fluidity and poor impact strength and a high-density polyethylene (HDPE) with high impact strength and the fluidity to be not good enough are blended to obtain a material which is good in impact strength and fluidity. The PP and the HDPE are good in resistance to solvents (dimethylbenzene, acetone and the like), nylon 6 can be added into the blending material so as to improve various performances, polarity of the material is improved, and a polyolefin elastomer (POE) is added simultaneously so as to achieve toughening modification. The macromolecular material can meet various requirements of solvent resistance, fluidity, impact strength and the like.
Description
Technical field
The present invention relates to a kind of macromolecular material, relate in particular to the polymer blended material of a kind of anti-solvent injection moulding, material can use in industries such as industrial chemicals storing, medicine, agricultural chemicals, food, daily use chemicals mainly for the preparation of the high polymer container of the packaging vessel of anti-solvent the and high impact high workability.
Background technology
Contain at present in the iron bucket of the Chemicals normal operation of solvent based spraying polyvinylidene difluoride (PVDF) (PVDF) coating and use, but coating easily comes off when using, cause content rotten, add that the coating operation is cumbersome, expense is obviously higher, and is uneconomical; Another is to use Glass Containers, and major defect can cause product leakage at carrying and cracky in transit, causes larger pollution; The material of common plastics bucket generally is PE and PP resin, but PE and PP bucket poor solvent resistance, swelling effect easily occurs, patent documentation (a kind of method that improves simultaneously Co-polypropylene shock strength and fluidity of molten for example, application number/patent No.: 200910081766), although satisfy high workability and high impact, but just be applicable to Co-polypropylene, be exactly poor solvent resistance and Co-polypropylene has the shortcoming of a maximum, especially industrial chemicals can cause the container swelling even break when temperature is higher, then cause the serious consequences such as leak of liquid, can't satisfy service requirements.
Summary of the invention
The present invention seeks to provides a kind of anti-solvent injection moulding with polymer blended material preparation method for addressing the above problem, prepared macromolecular material satisfies simultaneously high impact, high workability, solvent resistance and obtains larger raising, and be applicable to injection molding.
To achieve these goals, the present invention is achieved in that
The first step, the preparation of experimental raw:
Starting material are mainly: the polypropylene of melt flow rate (MFR) in 20g/10min ~ 30g/10min scope under the test condition of 230 ℃ and 2.16kg pressure, preferred PP 225, melt flow rate (MFR) MFR=26g/10min (test condition: 230 ℃, 2.16kg), manufacturer: the Nanjing noon and mould the industry company limited.
Under the test condition of 190 ℃ and 2.16kg pressure melt flow rate (MFR) 0.5g/10min ~ 4.0g/10min scope in notched Izod impact strength at 45KJ/m2 ~ 60KJ/m
2High density polyethylene(HDPE), preferred HDPE 5000S, (test condition: 190 ℃, 2.16kg), notched Izod impact strength is 45KJ/m to melt flow rate (MFR) MFR=0.9g/10min
2, manufacturer: raise sub-petrochemical industry.
Ethylene-octene copolymer, POE 8150, producer: du pont company.
Dicumyl peroxide (DCP), initiator, technical grade, Shanghai Gaoqiao petrochemical industry.
Antioxidant 1010, Nanjing Yangzi fine chemistry industry limited liability company.
Polyamide 6 (nylon 6), UBE Industries Ltd..
MALEIC ANHYDRIDE (MAH), analytical pure, the Long Huagongshijichang of Chengdu section.
Acetone, analytical pure, chemical agent company limited of traditional Chinese medicines group.
PP-g-MAH, polypropylene grafted maleic anhydride, self-control, prescription sees Table 1, and syntheti c route is as shown in Figure 1.
The prescription of table 1 preparation PP-g-MAH
| Title | Weight part |
| Polypropylene PP 225 | 500 |
| Antioxidant 1010 | 1.5 |
| Dicumyl peroxide (DCP) | 0.25 |
| MALEIC ANHYDRIDE (MAH) | 3 |
The used equipment of the present invention sees Table 2.
Table 2 major equipment
| Title | Model | The place of production |
| High-speed mixer (MAX8000 rev/min) | The ZRH-10 type | Fuxin City light industry mechanical ﹠ electrical equipment factory, Liaoning |
| Electric heating constant-temperature blowing drying box | The DHG-9140A type | The grand experimental installation of upper Nereid company limited |
| Electronic balance | The JY10001 type | The flat instrument of upper current chart company limited |
| Equidirectional parallel double-screw extruder | The SHJ-35 type | Nanjing extensively reaches rubber and plastics machine factory |
| The electronic type universal trier | WDT30 | Shenzhen triumphant strong sharp test apparatus company limited |
| Radial-boom impact tester | XJU-22 | Chengde trier factory |
| Plastic injection molding machine | HYF600 | Sea, Ningbo hawk plastics machinery company limited |
| The melt flow rate (MFR) trier | ZRZ-400 | The Shenzhen Sans Material Detection Co., Ltd |
The technological process of the preparation of PP-g-MAH and condition:
Accurately take by weighing PP, MAH, DCP and antioxidant 1010 by the prescription in the table 1, MAH is dissolved in the acetone, every 10ml acetone solution 3gMAH, first polypropylene is added high-speed mixer, the acetone solution thing, DCP and the antioxidant 1010 that add MAH start high-speed mixer and mix 2 minutes, after mixture is poured out, in stink cupboard, placed 5 minutes, for subsequent use.
Open twin screw extruder, set forcing machine each section temperature such as table 3, material is added material bin, start twin-screw extrusion machine host and frequency modulation rate to 10Hz, start reinforced motor, adjusting rotary speed is feeding rotating speed: 10Hz, material feeding, until the melting material extrude and enter from head normally extrude state after, with the extrudate check rod, pelletizing is for subsequent use behind water-cooled and wind cold drying.
Until material all extrude complete after, with acrylic resin extruder screw and barrel are cleared up, close successively reinforced power supply, main frame, each heating zone, close at last the forcing machine power supply.
Table 3 twin screw extruder is respectively distinguished temperature 1
| One district | Two districts | Three districts | Four districts | Five districts |
| 150℃ | 155℃ | 170℃ | 180℃ | 180℃ |
| Six districts | Seven districts | Eight districts | Nine districts | Head |
| 180℃ | 180℃ | 180℃ | 190℃ | 185℃ |
Second step, prepare anti-solvent injection moulding macromolecular material: principle is with good fluidity, homo-polypropylene (PP) and the imperfect high density polyethylene(HDPE) of shock strength high workability (HDPE) blend that shock strength is relatively poor, obtain all materials preferably of shock strength and flowability, solvent resistance (the dimethylbenzene of this bi-material (PP and HDPE) own, acetone etc.) better, in order further to improve properties, can also in blend, add nylon 6, increase the polarity of material, add simultaneously POE and carry out toughening modifying, but the amount of POE can not be many, because its solvent resistance is relatively poor, the many solvent resistances that can affect blend of amount.
The intermingling material of preparation is divided into two kinds, respectively according to the preparation of the prescription of table 4 and table 5, and the material solvent resistance that table 4 is prepared and bending strength ratio table 5 higher, but the shock strength of material, flowability and hardness ratio table 5 is slightly low.
The anti-solvent injection moulding of table 4 is weight part with Polymer materialspreparation prescription 1()
| PP 225 (part) | HDPE 5000S (part) | Ethylene-octene copolymer POE 8150 (part) | Antioxidant 1010 (part) |
| 25 | 75 | 5 | 0.3 |
The anti-solvent injection moulding of table 5 is weight part with Polymer materialspreparation prescription 2()
Accurately take by weighing various batchings by the prescription 4 and 5 in the table, mix with high-speed mixer, through the twin screw extruder extruding pelletization, and oven dry, the temperature in the forcing machine extrusion Zhong Ge district of table 4 correspondence sees Table 3, and the temperature in the forcing machine extrusion Zhong Ge district of table 5 correspondence sees Table 6.
Table 6 twin screw extruder is respectively distinguished temperature 2
| One district | Two districts | Three districts | Four districts | Five districts |
| 150℃ | 165℃ | 180℃ | 200℃ | 210℃ |
| Six districts | Seven districts | Eight districts | Nine districts | Head |
| 220℃ | 220℃ | 220℃ | 220℃ | 220℃ |
Owing to adopted above-mentioned measure, so the macromolecular material of employing method preparation can satisfy the requirements such as anti-solvent, flowability, shock strength.
Description of drawings
The syntheti c route synoptic diagram of Fig. 1 PP-g-MAH;
The SEM photo of the poyblend section of Fig. 2 the present invention preparation.
Embodiment
Testing standard:
The standard GB/T 1843-1996 of socle girder impact experiment;
The testing standard of flexural strength is GB/T 9341;
The oil absorbency test is carried out according to GB11547-89:
Universal sampling machine is cut into the sample of 5cm * 5cm, then puts into 50 ℃ of (high temperature) dimethylbenzene 1-2 weeks, takes out and dries surface solvent weighing (weighing is complete in 1 minute).Test solvent resistance advantage is that oil absorbency can reach capacity within a short period of time, has improved efficient under the high temperature.
Oil absorbency D (%) is calculated as follows:
D=（G2-G1）/G1?×100%
In the formula: the quality/g of sample behind G2-immersion oil
Quality/the g of sample before G1-immersion oil.
Embodiment 1
Accurately take by weighing various batchings by the prescription in the table 4, mix with high-speed mixer, through the twin screw extruder extruding pelletization, and oven dry, the temperature in the forcing machine extrusion Zhong Ge district of table 4 correspondence sees Table 3, and the properties test result of the macromolecular material of preparation sees Table 7, PP 30RA(Qilu Petrochemical in the table 7) be that enterprise is for the production of the polypropylene material of packaging vessel, be Co-polypropylene, through check, solvent resistance is not good; By the data in the contrast table 7, can find out that material solvent resistance corresponding to table 4 prescription obtained larger raising, shock strength and flowability are also suitable with PP 30RA, and flexural strength and Rockwell hardness improve more than PP 30RA.
The properties test result of the macromolecular material of table 7 preparation
Embodiment 2
Accurately take by weighing various batchings by the prescription in the table 5, mix with high-speed mixer, through the twin screw extruder extruding pelletization, and oven dry, the temperature in the forcing machine extrusion Zhong Ge district of table 5 correspondence sees Table 6, the properties test result of the macromolecular material of preparation sees Table 7, by the data in the contrast table 7, can find out that material solvent resistance corresponding to table 5 prescription obtained larger raising, more lower slightly than table 4 prescription, but shock strength, and flowability, flexural strength and Rockwell hardness increase than PP 30RA, especially mobile and Rockwell hardness improves more than PP 30RA, make electron-microscope scanning after the batten section that thrusts in the shock test is processed through metal spraying, the results are shown in shown in Figure 2, can find out that the interface is fuzzyyer, show that consistency is better between the system.
Claims (5)
1. polymer blended material of anti-solvent injection moulding, it is characterized in that: described intermingling material calculates by weight: melt flow rate (MFR) polipropene 25 part 20g/10min ~ 30g/10min scope under the test condition of 230 ℃ and 2.16kg pressure, under the test condition of 190 ℃ and 2.16kg pressure melt flow rate (MFR) in 0.5g/10min ~ 4.0g/10min scope with notched Izod impact strength at 45KJ/m
2~ 60KJ/m
275 parts of high density polyethylene(HDPE)s, 10 parts of ethylene-octene copolymers, 10 parts of polyamide 6s, 3 parts of polypropylene grafted maleic anhydrides, 0.3 part of antioxidant 1010; The preparation method of described polypropylene grafted maleic anhydride is: accurately take by weighing PP 500 weight parts, MAH 3 weight parts, DCP 0.25 weight part and antioxidant 1010 1.5 weight parts, MAH is dissolved in the acetone, every 10ml acetone solution 3gMAH, first polypropylene is added high-speed mixer, the acetone solution thing, DCP and the antioxidant 1010 that add MAH start high-speed mixer and mix 2 minutes, after mixture is poured out, in stink cupboard, placed 5 minutes, for subsequent use; Open twin screw extruder, set each section of forcing machine temperature, material is added material bin, start twin-screw extrusion machine host and frequency modulation rate to 10Hz, start reinforced motor, adjusting rotary speed is feeding rotating speed: 10Hz, material feeding, until the melting material extrude and enter from head normally extrude state after, with the extrudate check rod, pelletizing is for subsequent use behind water-cooled and wind cold drying.
2. the polymer blended material of a kind of anti-solvent injection moulding as claimed in claim 1, it is characterized in that: described polypropylene is PP 225, melt flow rate (MFR) MFR=26g/10min, test condition: 230 ℃, 2.16kg.
3. the polymer blended material of a kind of anti-solvent injection moulding as claimed in claim 1, it is characterized in that: described high density polyethylene(HDPE) is HDPE 5000S, melt flow rate (MFR) MFR=0.9g/10min, test condition: 190 ℃, 2.16kg notched Izod impact strength is 45KJ/m
2
4. the polymer blended material of a kind of anti-solvent injection moulding as claimed in claim 1, it is characterized in that: described ethylene-octene copolymer is POE 8150.
5. the polymer blended material of a kind of anti-solvent injection moulding as claimed in claim 1, it is characterized in that: described each section of setting forcing machine temperature refers to: a district, 150 ℃; Two districts, 155 ℃; Three districts, 170 ℃; Four districts, 180 ℃; Five districts, 180 ℃; Six districts, 180 ℃; Seven districts, 180 ℃; Eight districts, 180 ℃; Nine districts, 190 ℃; Head, 185 ℃.
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| CN 201110437659 CN102532660B (en) | 2011-12-23 | 2011-12-23 | Solvent-resistant macromolecular blending material for injection molding |
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|---|---|---|---|
| CN 201110437659 CN102532660B (en) | 2011-12-23 | 2011-12-23 | Solvent-resistant macromolecular blending material for injection molding |
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| CN102532660B true CN102532660B (en) | 2013-10-30 |
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| CN104610656A (en) * | 2015-01-29 | 2015-05-13 | 宝鸡石油机械有限责任公司 | High and low temperature resin material for plastic coating (impregnating) of steel wire ropes |
| CN105400053B (en) * | 2015-12-25 | 2018-06-19 | 广东威林工程塑料有限公司 | A kind of micro- permeability low viscosity PE alloy materials and preparation method thereof |
| CN107286294B (en) * | 2017-06-23 | 2019-12-31 | 常州大学 | Compatilizer for PP/PS extrusion molding and preparation method thereof |
| CN107880353B (en) * | 2017-11-22 | 2020-08-14 | 常州大学 | Solvent-resistant polymer composite material and preparation method and application thereof |
| CN108976596A (en) * | 2018-07-03 | 2018-12-11 | 江苏龙灯博士摩包装材料有限公司 | The plastic containers and preparation method thereof of high-purity chemicals dress filling |
| CN112391006A (en) * | 2020-11-12 | 2021-02-23 | 江苏金发科技新材料有限公司 | Wear-resistant self-lubricating polypropylene alloy composition and preparation method thereof |
| CN114672088A (en) * | 2022-04-12 | 2022-06-28 | 张瑞洋 | HDPE and PA blended foaming board |
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| CN101880416A (en) * | 2010-06-03 | 2010-11-10 | 潘少白 | Manufacturing method of flame retardant filter acid film on battery safety valve |
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| CN101880416A (en) * | 2010-06-03 | 2010-11-10 | 潘少白 | Manufacturing method of flame retardant filter acid film on battery safety valve |
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