CN107383678A - A kind of heat-resisting rigid plastics alloy granule of high-strength and high-transparent - Google Patents
A kind of heat-resisting rigid plastics alloy granule of high-strength and high-transparent Download PDFInfo
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- CN107383678A CN107383678A CN201710609972.4A CN201710609972A CN107383678A CN 107383678 A CN107383678 A CN 107383678A CN 201710609972 A CN201710609972 A CN 201710609972A CN 107383678 A CN107383678 A CN 107383678A
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to a kind of heat-resisting rigid plastics alloy granule of high-strength and high-transparent, it is in parts by weight 100 parts of 700 Corvic including the degree of polymerization, 15~25 parts of 400 Corvic of the degree of polymerization, 7~9 parts of methacrylate butadiene styrol copolymer, 10~15 parts of maleic anhydride grafted ethene octene copolymer elastomer, amino modified 1.5~2.0 parts of graphene oxide, 1.5~2.2 parts of methacrylate processing aid, 1.8~2.5 parts of thiol methyl tin, 2.4~2.6 parts of butyl laurate, 0.25~0.35 part of stearic acid, 0.2~0.3 part of OPE, three (2, 4 dibromobenzenes) phosphoesterase 30 .15~0.2 part, 0.1~0.2 part of aluminate coupling agent, hyacinthine pigment is micro.The present invention has the high grade of transparency, excellent physical mechanical performance concurrently and using processing characteristics, has good market application foreground.
Description
Technical field
The present invention relates to a kind of plastic alloy pellet, more particularly to a kind of heat-resisting rigid plastics alloy granule of high-strength and high-transparent
Material, belongs to polymer alloy material technical field.
Background technology
Polyvinyl chloride resin (polyvinyl chloride) is used as general-purpose plastics, price and modified workability due to its relative moderate
And it is widely used in varieties of food items packaging, medical packaging, cosmetic package, household electrical appliance packaging, auto parts machinery, chemical industry material
The field such as material, building decoration building materials, fire-fighting equipment accessory, sanitary ware, supermarket shelves.Modified PVC granule product is universal at present
Exist single product structure, product specification and it is with low content of technology the problems such as, its combination property oneself far can not meet plastic products
Production industry user's request with rapid changepl. never-ending changes and improvements, seriously constrains the development of China's modified PVC and relevant industries.Realize general-purpose plastics
PVC high performance is to improve the effective means that PVC is modified industry viability and competitiveness, and PVC alloyings are high performances
Effective way, such as using PVC/ABS alloys as representative.
But, can be to hard PVC pellet due to the addition of various auxiliary agents in PVC alloys and the influence of polyvinyl chloride resin quality itself
Transparency produce large effect, particularly in injection moulding process, due to moment point can be produced when material flows through runner at a high speed
High frictional force between son, the phenomenon of material discoloration or zoom is easily produced, universal method is that phase is added in material prescription at this stage
To excessive general in-lubricant (such as：Tristerin) rubbed to reduce intermolecular height of this moment, and just because of this
The addition of the excessive general in-lubricant of kind generates considerable influence to transparency, so as to seriously limit PVC alloy injection-molded items
Application.In addition, the progress with plastics-production process technology and the continuous lifting to product performance demands, are developed same
When with excellent physical mechanical performance and using processing characteristics PVC plastic alloy granule also turn into current plastic products give birth to
Produce the urgent expectation of processing enterprise.
The content of the invention
Studied and improved for drawbacks described above, applicant existing for existing PVC plastic alloy, it is desirable to provide Yi Zhonggao
The heat-resisting rigid plastics alloy granule of intensity high transparency, to realize above-mentioned technical purpose, the present invention uses following scheme：
A kind of heat-resisting rigid plastics alloy granule of high-strength and high-transparent, in parts by weight including following components：
Wherein, in terms of VOC content %：The polyvinyl chloride tree that the Corvic and the degree of polymerization that the degree of polymerization is 700 are 400
Fat≤0.03%, metacrylate-butadiene-styrene VOC≤0.02%, maleic anhydride grafted ethene-octene copolymer
Elastomer VOC≤0.03%, butyl laurate VOC≤0.03%；
Its preparation method is as follows：
The Corvic for being first 400 by Corvic and the degree of polymerization that the degree of polymerization is 700, the methyl
Acrylate-butadiene-styrol copolymer, the maleic anhydride grafted ethene-octene copolymer elastomer add high speed heat
Mixer carries out high-speed stirred；Add the amino modified graphene oxide, the methacrylate processing aid, described
Thiol methyl tin, the butyl laurate, the stearic acid, the OPE, the coupling agent and the hyacinthine
Pigment adds high speed thermal agitation machine；Be eventually adding three (2,4- dibromobenzene) phosphates, high-speed kneading to 120~125 DEG C of dischargings, then
It is put into low speed cooling mixer and is cooled to normal temperature, obtains mixed powder；Above-mentioned mixed powder is put into double-screw extruding pelletizing machine
It is granulated, is produced.
Preferably, above-mentioned alloy granule includes following components in parts by weight：
Preferably, amino modified graphene oxide is selected from triethylene tetramine modified graphene oxide and/or ethylenediamine changes
Property graphene oxide.
Preferably, in terms of VOC content %, methacrylate processing aid VOC≤0.04%.
Preferably, in terms of VOC content %, stearic acid VOC≤0.02%, the OPE VOC≤
0.03%.
Preferably, the drop temperature is 122 DEG C.
Preferably, the double-screw extruding pelletizing machine uses Φ 80PVC conical double-screw extruding granulators, its process warm
Degree control is 155~185 DEG C, 35 revs/min of main-machine screw rotating speed, 30 revs/min of feed-screw rotating speed.
The technical effects of the invention are that：
Present invention applicant passes through the compatible system with cooperative effect on the basis of general PVC resin components system
Design and optimization, one kind is developed by degree of polymerization P700/P400 Corvics, metacrylate-butadiene-styrene
The plastic alloy that the raw material such as copolymer and maleic anhydride grafted ethene-octene copolymer elastomer forms according to special ratios blending
Pellet, by being controlled utilization to various additives and its proportioning, especially creatively selection with the addition of the ammonia of specific proportioning
Base modified graphene oxide and butyl laurate；Amino modified graphene oxide and have between resinous polymer group strong
Chemical bond, performance test data proves that modeling can be significantly improved by adding the amino modified graphene oxide of special ratios
Expect the tensile strength and heat endurance of alloy, contribute to the raising of plastic alloy entirety physical and mechanical properties；Butyl laurate is made
For the in-lubricant of resinous polymer, coordinate stearic acid and the combination of OPE inside and outside lubricant agent, resin can be significantly reduced
The shearing internal friction of material and the release property with metal die, while product mobility and surface gloss can be improved, again
Because butyl laurate self character is minimum on the influence of PVC alloy products transparency, can effectively be subtracted by suitably increasing its dosage
Internal friction of the small PVC alloy products in injection, make to be moulded in and ultra-high transparency and surface are completed and obtained in very short time
Glossiness；Aluminate coupling agent contains can be with the group of active hydrogen reaction, thus can be with hydroxyl, carboxyl or surface adsorption water
Bonding action occurs for inorganic filler, improves the compatibility and adhesion of amino modified graphene oxide and resin system, can also carry
High-adhesive-strength；It is aided with high-impact MBS ternary graft copolymers, methacrylate
Processing aid and thiol methyl tin heat stabilizer, with three (2,4- dibromobenzene) phosphates as fire retardant, effectively increase PVC conjunctions
The erosion-resisting characteristics of golden material is simultaneously favorably improved product transparency, can advantageously promote the gelation and plasticizing of PVC alloys；Add
Micro hyacinthine pigment can improve micro- yellow true qualities of PVC alloys to assign product more preferable apparent visual effect.Meanwhile applicant
It has also been found that, P700/P400 Corvics, metacrylate-butadiene-styrene, maleic anhydride are connect by research
When the VOC content of branch ethylene-octene copolymer elastomer and butyl laurate be strict controlled under certain proportion, energy
Further improve the transparency of PVC alloy products.
To sum up, a kind of substituted for plastic alloy product of the plastic alloy pellet of the present invention as current PVC/ABS alloys, has concurrently
The high grade of transparency, excellent physical mechanical performance and using processing characteristics, have good market application foreground.
Embodiment
Describe the embodiment of the present invention in detail below by specific embodiment, but not to the claim of the present invention
Do any restriction.
Specified otherwise that such as it's too late, each raw material involved by following examples is the commercially available universal product, and involved each production is set
Standby is this area conventional equipment.
The plastic alloy pellet each group distribution ratio of 1~embodiment of embodiment 4 is referring to table 1.
The plastic alloy pellet each component weight proportion (unit of 1 1~embodiment of embodiment of table 4：Kilogram)
1~embodiment of embodiment 2 is VOC content (%) control group, and its each component VOC content is referring to table 2；Embodiment 3~
Embodiment 4 is control group.
The plastic alloy pellet each component VOC content (%) of 2 1~embodiment of embodiment of table 2
The specific preparation method of the plastic alloy granule product of 1~embodiment of embodiment 4 is as follows：
(1) according to raw material proportioning shown in Tables 1 and 2 and VOC content requirement, first by the degree of polymerization be 700 polyvinyl chloride tree
The Corvic, methacrylate butadi ene styrene copolymer, maleic anhydride that fat and the degree of polymerization are 400 are grafted second
Alkene-octene copolymer elastomer adds high speed thermal agitation machine and carries out high-speed stirred；Add triethylene tetramine modified graphite oxide
Alkene, methacrylate processing aid, thiol methyl tin, butyl laurate, stearic acid, OPE, coupling agent and purple
Blue pigment adds high speed thermal agitation machine；Be eventually adding three (2,4- dibromobenzene) phosphates, high-speed kneading to 122 DEG C of dischargings, then
It is put into low speed cooling mixer and is cooled to normal temperature, obtains mixed powder.
Wherein, triethylene tetramine modified graphene oxide preparation method is as follows：Prepared and aoxidized using improved Hummers methods
Graphite, 250mg graphite oxides are added in 250mL DMF, are ultrasonically treated 3h, obtain graphene oxide suspension, add 35g TETA,
7g Dicyclohexylcarbodiimides, ultrasonic 10min, 48h is reacted at 120 DEG C, 75ml absolute ethyl alcohols is added, stands overnight, in removing
Layer clear liquid, with polytetrafluoroethylene (PTFE) membrane filtration lower sediment, and washs precipitation, in 65 DEG C of dryings with ethanol, deionized water.
(2) above-mentioned mixed powder is put into the feeding hopper of Φ 80PVC conical double-screw extruding granulators, then passes through feeding
The quantifying feed screw rod of bucket, be quantitatively adding in Φ 80PVC conical double-screw extruding granulators and be granulated, earnestly after pellet give
To air-cooled bobbing machine, storage bin is entered after being cooled to less than 40 DEG C, quantitative package, finished product are carried out after storing.
Φ 80PVC conical double-screw extruding granulator comminutor running parameters are：155~185 DEG C of temperature, main-machine screw turn
35 revs/min of speed, 30 revs/min of feed-screw rotating speed.
The made plastic alloy pellet physical and mechanical properties test result of 1~embodiment of embodiment 4 is referring to table 3.
The physical and mechanical properties test result of table 3
From the test data of table 3, compared with commercially available similar plastic alloy granule product, 1~embodiment of embodiment 4 is made
Plastic alloy pellet have considerably higher transparency and more excellent physical and mechanical properties (tensile strength, bending strength) with
And heat endurance；Meanwhile if by the Corvic in alloy granule, metacrylate-butadiene-styrene copolymerized
VOC content in thing, maleic anhydride grafted ethene-octene copolymer elastomer and butyl laurate is controlled under certain proportion
When, it will further improve the transparency of alloy granule.
Embodiment provided above is the better embodiment of the present invention, is only used for the convenient explanation present invention, not to this hair
It is bright to make any formal limitation, any those of ordinary skill in the art, if putting forward skill not departing from the present invention
In the range of art feature, using the equivalent embodiment locally changed or modified made by disclosed technology contents, and
Without departing from the technical feature content of the present invention, in the range of still falling within the technology of the present invention feature.
Claims (7)
- A kind of 1. heat-resisting rigid plastics alloy granule of high-strength and high-transparent, it is characterised in that：Include following components in parts by weight：Wherein, in terms of VOC content %：The Corvic that the Corvic and the degree of polymerization that the degree of polymerization is 700 are 400≤ 0.03%, metacrylate-butadiene-styrene VOC≤0.02%, maleic anhydride grafted ethene-octene copolymer elasticity Body VOC≤0.03%, butyl laurate VOC≤0.03%；Its preparation method is as follows：The Corvic for being first 400 by Corvic and the degree of polymerization that the degree of polymerization is 700, the metering system Acid esters-BS, the maleic anhydride grafted ethene-octene copolymer elastomer add high speed thermal agitation Machine carries out high-speed stirred；Add the amino modified graphene oxide, the methacrylate processing aid, the mercaptan Methyl tin, the butyl laurate, the stearic acid, the OPE, the coupling agent and the hyacinthine pigment Add high speed thermal agitation machine；Three (2,4- dibromobenzene) phosphates are eventually adding, high-speed kneading places into 120~125 DEG C of dischargings Low speed cooling mixer is cooled to normal temperature, obtains mixed powder；Above-mentioned mixed powder input double-screw extruding pelletizing machine is carried out It is granulated, produces.
- 2. the heat-resisting rigid plastics alloy granule of high-strength and high-transparent according to claim 1, it is characterised in that：With parts by weight Meter includes following components：
- 3. the heat-resisting rigid plastics alloy granule of high-strength and high-transparent according to claim 1, it is characterised in that：It is amino modified Graphene oxide is selected from triethylene tetramine modified graphene oxide and/or ethylenediamine modified graphene oxide.
- 4. the heat-resisting rigid plastics alloy granule of high-strength and high-transparent according to claim 1, it is characterised in that：Contained with VOC Measure % meters, methacrylate processing aid VOC≤0.04%.
- 5. the heat-resisting rigid plastics alloy granule of high-strength and high-transparent according to claim 1, it is characterised in that：Contained with VOC Measure % meters, stearic acid VOC≤0.02%, OPE VOC≤0.03%.
- 6. the heat-resisting rigid plastics alloy granule of high-strength and high-transparent according to claim 1, it is characterised in that：The discharging Temperature is 122 DEG C.
- 7. the heat-resisting rigid plastics alloy granule of high-strength and high-transparent according to claim 1, it is characterised in that：Double spiral shells Bar extruding granulator uses Φ 80PVC conical double-screw extruding granulators, and the control of its technological temperature is 155~185 DEG C, main frame spiral shell 35 revs/min of bar rotating speed, 30 revs/min of feed-screw rotating speed.
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| CN201710609972.4A CN107383678A (en) | 2017-07-24 | 2017-07-24 | A kind of heat-resisting rigid plastics alloy granule of high-strength and high-transparent |
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| CN201710609972.4A CN107383678A (en) | 2017-07-24 | 2017-07-24 | A kind of heat-resisting rigid plastics alloy granule of high-strength and high-transparent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250969A (en) * | 2020-10-24 | 2021-01-22 | 杭州富阳龙翔塑料制品有限公司 | High-transparency plastic particles for shoemaking and preparation process thereof |
| CN114149647A (en) * | 2021-12-30 | 2022-03-08 | 深圳恒方大高分子材料科技有限公司 | High-transparency high-heat-resistance medical hard PVC alloy material |
| CN115975392A (en) * | 2023-01-07 | 2023-04-18 | 山东维克曼新材料有限公司 | High-strength wear-resistant wood-plastic new material and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250969A (en) * | 2020-10-24 | 2021-01-22 | 杭州富阳龙翔塑料制品有限公司 | High-transparency plastic particles for shoemaking and preparation process thereof |
| CN112250969B (en) * | 2020-10-24 | 2022-07-15 | 杭州富阳龙翔塑料制品有限公司 | High-transparency plastic particles for shoemaking and preparation process thereof |
| CN114149647A (en) * | 2021-12-30 | 2022-03-08 | 深圳恒方大高分子材料科技有限公司 | High-transparency high-heat-resistance medical hard PVC alloy material |
| CN115975392A (en) * | 2023-01-07 | 2023-04-18 | 山东维克曼新材料有限公司 | High-strength wear-resistant wood-plastic new material and preparation method thereof |
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