CN106700342A - Injection molding grade PVC composite material high in mobility and melt strength - Google Patents
Injection molding grade PVC composite material high in mobility and melt strength Download PDFInfo
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- CN106700342A CN106700342A CN201611209282.1A CN201611209282A CN106700342A CN 106700342 A CN106700342 A CN 106700342A CN 201611209282 A CN201611209282 A CN 201611209282A CN 106700342 A CN106700342 A CN 106700342A
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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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
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- C08K2201/011—Nanostructured additives
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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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Abstract
The invention relates to an injection molding grade PVC composite material high in mobility and melt strength and belongs to the technical field of macromolecules. The composite material comprises, by weight parts, 30-60 parts of low molecular weight PVC resin powder, 5-20 parts of crosslinking PVC resin powder, 10-30 parts of main plasticizer, 10-20 parts of secondary plasticizer, 0.5-20 parts of nano calcium carbonate, 0.5-2 parts of high melt strength processing agent, 0.4-1.5 parts of lubricant, 0.5-4 parts of heat stabilizer, 0.1-1 part of light stabilizer, 0.1-0.3 part of antioxidant and 1-3 parts of other auxiliaries. Melt strength and mechanical properties of the PVC composite material are improved while high mobility is guaranteed. The injection molding grade PVC composite material can adapt to injection molding products of various sizes and shapes and can meet requirements of low plastic temperature and short plastic cycle.
Description
Technical field
The present invention relates to a kind of high fluidity and the injection grade PVC composites of high fondant-strength, belong to Polymer Technology
Field.
Background technology
PVC is the english abbreviation of polyvinyl chloride, and PVC modified materials are cheap, abundant raw material, and simple processing in automobile, is built
Build, the industry such as household electrical appliances and cable is widely used, be one of maximum plastics of yield in the world at present.And injection molding technology is modeling
Expect a kind of most common means of machine-shaping, with continuing to develop for injection molding technology, Shooting Technique constantly pursues lower injection
Temperature and shorter injection cycle, to reduce energy consumption and improve production capacity.Therefore, the requirement to injected plastics material is also improved constantly, with
Meet low temperature and the injection of short cycle.But the product of conventional PVC injection mouldings is easily occurring outside tiger fur line, crackle and contraction etc.
See bad phenomenon.Conventional solution has (one) that the lower polyvinyl chloride resin of molecular weight or addition lubricant are selected in terms of material, with
Improve the mobility of material；(2) in terms of mold design, it is molded using many cast gates and hot flow path as far as possible, material is improved by mould
Material mobility in a mold.Two methods can improve mobility, and aesthetic appearance defect is solved by high fluidity.With existing
In the complication of auto-parts and other injecting products, the size and dimension of product is changeful, and particularly some spies are small-sized
Or the design of super-large product (such as microminiature quarter window and ultra-large type quarter window) and product variable cross-section, in addition to low injection temperature
Degree and the pursuit in short modeling cycle, lot of challenges is brought to PVC injected plastics materials.It is simple to be set by improving mobility or adjustment mould
Meter, has been difficult to solve the open defect of injection and has ensured production stability.In order to reduce this risk, it is necessary to ensureing PVC materials
On the basis of material high fluidity, the melt strength of PVC material is improved.
The content of the invention
The present invention provides a kind of for above-mentioned problem while the injection grade PVC with high fluidity and high fondant-strength is answered
Condensation material, the composite also has preferable mechanical property.
Above-mentioned purpose of the invention is achieved through the following technical solutions：A kind of injection grade of high fluidity and high fondant-strength
PVC composites, described composite includes the component of following parts by weight：30-60 parts of low-molecular-weight PVC resin powder, friendship
5-20 parts of PVC resin powder of connection, primary plasticizer 10-30 parts, extender plasticizer 10-20 parts, nano-calcium carbonate 0.5-20 parts, melt high
0.5-2 parts of intensity processing aid, lubricant 0.4-1.5 parts, heat stabilizer 0.5-4 parts, light stabilizer 0.1-1 parts, antioxidant
0.1-0.3 parts, 1-3 parts of other auxiliary agents.
The present invention is added from appropriate low-molecular-weight PVC resin powder with a small amount of crosslinked PVC resin-oatmeal compatibility, not only can be with
The mobility of composite is improved, the melt strength of composite and the glossiness of reduction material can also be improved.With both
Polyvinyl chloride resin is matrix, rounded, and surface is simultaneously rough, there is substantial amounts of fold, and its reason is a large amount of of nano-calcium carbonate
Filling causes that the volume of PVC granule tends to full, and shape is also homogeneous.Because nano-calcium carbonate is with than more uniform nanoscale point
It has been scattered among the particle of PVC, and the Surface coating of nano-calcium carbonate layer of surface modifying agent so that hydrophily drops significantly
It is low, while being greatly improved with the associativity and wetability of organic matter；Therefore, there are a large amount of folds in the surface of polyvinyl chloride resin particle, and
Modified nano-calcium carbonate can be well dispersed in polyvinyl chloride resin, and good strengthening action is produced to PVC matrix.In the present invention
Also coordinate in composite and be added with primary plasticizer and extender plasticizer, further improve the heat resistance of composite, prevent
Degradeds of the PVC in injection moulding process.
The degree of polymerization of described low-molecular-weight PVC resin powder is 800-1100.This scope polymer P VC resin-oatmeal, i.e., really
The high fluidity of PVC material is protected, it may have the high fondant-strength processing aid in good melt strength, with composite is produced
Raw synergy is more beneficial for the processing of material.
Described crosslinked PVC resin-oatmeal is chemical crosslinking PVC resin powder of the gel content in 20%-50%.This scope is coagulated
The PVC resin powder of glue content, with melt strength higher, while excessive negative effect will not be caused to high fluidity.
Described primary plasticizer is diisononyl phthalate and/or didecyl phthalate.
Described extender plasticizer is diisooctyl adipate, trimellitic acid dioctyl ester, DOTP, epoxy
One or more in soybean oil.If in the present invention without extender plasticizer, only primary plasticizer, to PVC material
Heat resistance and cold resistance can cause larger negative effect.
Described nano-calcium carbonate is that, by wet-process modified obtained modified nano calcium carbonate, specific method is：By nanometer
Calcium carbonate is configured to suspension, the constant speed stirring in 60-75 DEG C of water-bath, is slowly added to surface modifier, is cooled down after stirring 1-2h,
Through filtering, drying, sieving, then with tetrahydrofuran backflow extracting 2-4h, remove the surface modifier of physical absorption.
The particle diameter of surface modified nano calcium carbonate is small, specific surface area increase, thus increases with matrix resin contact area.When
When being acted on by external force, rigid Nano particles of calcium carbonate causes matrix resin crazing energy absorption, so as to reach to polyvinyl chloride resin
The effect of toughness reinforcing.
Further preferably, described surface modifier is one or more in stearic acid, aluminate, titanate ester.
Preferably, particle diameter accounts for 50-60% for the particle of 20-80nm in described modified nano calcium carbonate, particle diameter is 80-
The particle of 100nm accounts for 40-50%.
Described high fondant-strength processing aid is acrylic resin processing aid.If in the present invention from raising melt
The plasticizer of intensity can then have a strong impact on the hardness and processing characteristics of PVC, and then cause the composite cannot to meet while having
The requirement of high fluidity, high fondant-strength and excellent in mechanical performance.
Described lubricant is one or more in stearic acid, PE waxes, PPA.
Described lubricant combination is (1-2) by PE waxes, stearic acid, PPA in mass ratio：(1-2):0.1 compounding is formed.PE
Wax effectively alleviates the degraded of PP as interior lubrication, and stearic acid, PPA in material production application, are played as outer lubrication
Surface lubrication, improves product surface sophistication.The lubricant of compounding is added in PVC material, all components can be reduced
Mixing internal friction when adding so that component is well mixed, improving product properties, while reduce plastics being set with machining
Frictional force between standby, prevents PVC material to be bonded on metal-working plant, improves equipment production intensity.By various lubricants
It is applied in combination, can reach more preferable effect.
Described heat stabilizer is calcium-zinc composite stabilizing agent and/or barium zinc stabilizer.
Described light stabilizer is UV-531, UV-9, UV-326, UV-P, UV-24, UV-2908, triazine -5, hindered amine light
One or more of stabilizer.
Described antioxidant is bisphenol-A, antioxidant CA, antioxidant 264, antioxidant 2246, antioxidant 1076, antioxidant
One or more in 168.
Other described auxiliary agents include toner, color masterbatch.
In the injection grade PVC composites of above-mentioned high fluidity and high fondant-strength, described composite also includes
1-5 parts of rubber modifier.
Preferably, described rubber modifier is in nitrile rubber, styrene/butadiene rubbers, organic silicon rubber
One or more.Make rubber modifier from diene rubber in the present invention, further improve toughness, the bullet of PVC composites
Property and melt strength.
In the injection grade PVC composites of above-mentioned high fluidity and high fondant-strength, described composite also includes
2-8 parts of anti-impact modifier.
Preferably, described anti-impact modifier is one or more in MBS, CPE, ABS, EVA, ACR, NBR.Enter
Preferably, described anti-impact modifier is CPE, ACR to one step.Loading with impact modifier increases, and impact (breach) is strong
Angle value is incremented by, and CPE, ACR are linear, and overall target preferably, and has critical value, meets the multiple crazing of increasing tougheness theoretical.It is i.e. outer
Under power effect, formed in PVC and modifying agent two-phase (or multiphase) interface of good combination, PVC produces fine crack and involves
Rubbery state particle, makes its compression, produces stress concentration, induces a large amount of crazings and shear band, absorbs and the most of energy of consumption
Amount；Again because rubber particles are present, crazing can be controlled to develop, prevent it from turning into destructive crackle, toughening effect becomes strong, body
It is that impact strength is improved, it is more notable to improving the effect of non-notch impact strength.Wherein, impact modifier ACR is by propylene
Acid butyl ester (BA), methyl methacrylate (MMA) are reacted by multi-step emulsion polymerization and formed, and core is polymerized to the BA being crosslinked, with
PVC compatibilities it is good be polymerized to shell such as MMA, multi-element graft copolymer of the composition with " core-shell structure copolymer " structure.Due to the dissolving of MMA
Degree is close with PVC, and by itself plus people to PVC, the two can form uniform continuous phase.And ACR is then scattered in PVC with particle shape
In continuous phase matrix, unique " sea-island " structure is formed, the impact modifier of this structure is more conform with crazing-shear band reason
The toughening mechanism of opinion.
Compared with prior art, composite of the present invention is with appropriate low-molecular-weight polyvinyl chloride resin and a small amount of crosslinked PVC resin
It is matrix, the volume of PVC granule is tended to full by the filling of modified nano-calcium carbonate, and coordinate other components, such as
Lubricant, high fondant-strength processing aid and rubber modifier, anti-impact modifier etc., on the basis for ensuring high fluidity
On, improve the melt strength and mechanical property of PVC composites.Injection grade PVC composites of the invention are adapted to various
The injecting products of different sizes and shapes, and low modeling temperature and the short modeling cycle can be met.
Specific embodiment
The following is specific embodiment of the invention, technical scheme is further described, but the present invention is simultaneously
It is not limited to these embodiments.
Table 1：The component of injection grade PVC composites in embodiment 1-5
Embodiment 1-5
By the component dispensing of the injection grade PVC composites described in the embodiment 1-5 of table 1, by conventional injection molding
Technique can be prepared by the injection grade PVC composites of high fluidity of the invention and high fondant-strength.
Comparative example 1
The comparative example does not contain modified nano calcium carbonate with differing only in for embodiment 5.
Comparative example 2
The comparative example does not contain acrylic resin processing aid with differing only in for embodiment 5.
Comparative example 3
The comparative example differs only in the non-modified treatment of nano-calcium carbonate with embodiment 5, and particle diameter is less than 20nm.
Comparative example 4
The comparative example differs only in the non-modified treatment of nano-calcium carbonate with embodiment 5, and particle diameter is higher than 100nm.
Comparative example 5
The comparative example is homogeneous common polyvinyl chloride resin with the PVC differed only in the comparative example of embodiment 5.
In the above-described embodiments, the degree of polymerization of low-molecular-weight PVC resin powder is 800-1100；Crosslinked PVC resin-oatmeal is solidifying
Chemical crosslinking PVC resin powder of the glue content in 20%-50%.Nano-calcium carbonate is by wet-process modified obtained modified Nano carbon
Sour calcium, specific method is：Nano-calcium carbonate is configured to suspension, constant speed stirring, is slowly added to surface in 60-75 DEG C of water-bath
Modifying agent (can be one or more in stearic acid, aluminate, titanate ester), cools down after stirring 1-2h, through filtering, dries
Dry, sieving, then with tetrahydrofuran backflow extracting 2-4h, remove the surface modifier of physical absorption.And described modified Nano carbon
Particle diameter accounts for 50-60% for the particle of 20-80nm in sour calcium, and particle diameter accounts for 40-50% for the particle of 80-100nm.Heat stabilizer can be with
It is calcium-zinc composite stabilizing agent and/or barium zinc stabilizer.Light stabilizer can for UV-531, UV-9, UV-326, UV-P, UV-24,
UV-2908, triazine -5, one or more of hindered amine as light stabilizer.Antioxidant can be bisphenol-A, antioxidant CA, antioxidant
264th, one or more in antioxidant 2246, antioxidant 1076, irgasfos 168.Other auxiliary agents include toner, color masterbatch.Rubber
Modifying agent can be one or more in nitrile rubber, styrene/butadiene rubbers, organic silicon rubber.Anti-impact modifier
Can be one or more in MBS, CPE, ABS, EVA, ACR, NBR.
Injection grade PVC composites in embodiment 1-5 and comparative example 1-4 are cut into water bar carries out performance test, test knot
Fruit is as shown in table 2.
Table 2：The performance of the injection grade PVC composites in embodiment 1-5 and comparative example 1-4
Wherein melt strength detects that die entrance angle is 30 using capillary rheometer:1, shear rate is 5mm/s.
As known from Table 2, composite of the present invention is with appropriate low-molecular-weight polyvinyl chloride resin and a small amount of crosslinked PVC resin as base
Body, makes the volume of PVC granule tend to full by the filling of modified nano-calcium carbonate, and coordinates other components, such as lubricates
Agent, high fondant-strength processing aid and rubber modifier, anti-impact modifier etc., on the basis of high fluidity is ensured, carry
The melt strength and mechanical property of high PVC composite.Injection grade PVC composites of the invention are adapted to various different chis
The injecting products of very little and shape, and low modeling temperature and the short modeling cycle can be met.
Specific embodiment described herein is only to the spiritual explanation for example of the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be substituted using similar mode, but simultaneously
Do not deviate by spirit of the invention or surmount scope defined in appended claims.
It is skilled to this area although having made a detailed description and being cited some specific embodiments to the present invention
For technical staff, as long as it is obvious that can be made various changes without departing from the spirit and scope of the present invention or corrected.
Claims (10)
1. a kind of injection grade PVC composites of high fluidity and high fondant-strength, it is characterised in that described composite bag
Include the component of following parts by weight：30-60 parts of low-molecular-weight PVC resin powder, 5-20 parts of crosslinked PVC resin-oatmeal, primary plasticizer 10-
30 parts, extender plasticizer 10-20 parts, nano-calcium carbonate 0.5-20 parts, 0.5-2 parts of high fondant-strength processing aid, lubricant
0.4-1.5 parts, heat stabilizer 0.5-4 parts, light stabilizer 0.1-1 parts, antioxidant 0.1-0.3 parts, 1-3 parts of other auxiliary agents.
2. injection grade PVC composites of high fluidity according to claim 1 and high fondant-strength, it is characterised in that
The degree of polymerization of described low-molecular-weight PVC resin powder is 800-1100, and described crosslinked PVC resin-oatmeal exists for gel content
The chemical crosslinking PVC resin powder of 20%-50%.
3. injection grade PVC composites of high fluidity according to claim 1 and high fondant-strength, it is characterised in that
Described primary plasticizer is diisononyl phthalate and/or didecyl phthalate, and described extender plasticizer is for oneself
One or more in diacid di-isooctyl, trimellitic acid dioctyl ester, DOTP, epoxidized soybean oil.
4. injection grade PVC composites of high fluidity according to claim 1 and high fondant-strength, it is characterised in that
Described nano-calcium carbonate is that, by wet-process modified obtained modified nano calcium carbonate, specific method is：Nano-calcium carbonate is matched somebody with somebody
Suspension is made, the constant speed stirring in 60-75 DEG C of water-bath is slowly added to surface modifier, is cooled down after stirring 1-2h, through filtering,
Drying, sieving, then with tetrahydrofuran backflow extracting 2-4h, remove the surface modifier of physical absorption.
5. injection grade PVC composites of high fluidity according to claim 4 and high fondant-strength, it is characterised in that
Particle diameter accounts for 50-60% for the particle of 20-80nm in described modified nano calcium carbonate, and particle diameter accounts for 40- for the particle of 80-100nm
50%.
6. injection grade PVC composites of high fluidity according to claim 1 and high fondant-strength, it is characterised in that
Described high fondant-strength processing aid is acrylic resin processing aid, and described lubricant is in stearic acid, PE waxes, PPA
One or more.
7. injection grade PVC composites of high fluidity according to claim 1 and high fondant-strength, it is characterised in that
Described composite also includes 1-5 parts of rubber modifier.
8. injection grade PVC composites of high fluidity according to claim 7 and high fondant-strength, it is characterised in that
Described rubber modifier is one or more in nitrile rubber, styrene/butadiene rubbers, organic silicon rubber.
9. injection grade PVC composites of high fluidity according to claim 1 and high fondant-strength, it is characterised in that
Described composite also includes 2-8 parts of anti-impact modifier.
10. injection grade PVC composites of high fluidity according to claim 9 and high fondant-strength, it is characterised in that
Described anti-impact modifier is one or more in MBS, CPE, ABS, EVA, ACR, NBR.
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| CN107639912A (en) * | 2017-09-28 | 2018-01-30 | 江苏凤腾塑料有限公司 | A kind of compound PVC board |
| CN111058294A (en) * | 2018-10-17 | 2020-04-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Skin layer composition, foamed layer composition and low-odor PVC artificial leather prepared from same |
| CN112831140A (en) * | 2021-01-29 | 2021-05-25 | 福建省民爆化工股份有限公司 | Preparation and application methods of integrated injection molding material |
| CN113121931A (en) * | 2021-03-11 | 2021-07-16 | 四川省金路树脂有限公司 | High-fluidity injection molding grade PVC composite material and preparation method thereof |
| CN116355328A (en) * | 2023-04-17 | 2023-06-30 | 浙江富华新材料科技有限公司 | Composition of heat-resistant and oxidation-resistant PVC particles and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107639912A (en) * | 2017-09-28 | 2018-01-30 | 江苏凤腾塑料有限公司 | A kind of compound PVC board |
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| CN111058294A (en) * | 2018-10-17 | 2020-04-24 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Skin layer composition, foamed layer composition and low-odor PVC artificial leather prepared from same |
| CN112831140A (en) * | 2021-01-29 | 2021-05-25 | 福建省民爆化工股份有限公司 | Preparation and application methods of integrated injection molding material |
| CN113121931A (en) * | 2021-03-11 | 2021-07-16 | 四川省金路树脂有限公司 | High-fluidity injection molding grade PVC composite material and preparation method thereof |
| CN116355328A (en) * | 2023-04-17 | 2023-06-30 | 浙江富华新材料科技有限公司 | Composition of heat-resistant and oxidation-resistant PVC particles and preparation method thereof |
| CN116355328B (en) * | 2023-04-17 | 2023-10-27 | 浙江富华新材料科技有限公司 | Composition of heat-resistant and oxidation-resistant PVC particles and preparation method thereof |
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