CN106589670A - Hard PVC coloring master batch and preparation method thereof - Google Patents

Hard PVC coloring master batch and preparation method thereof Download PDF

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Publication number
CN106589670A
CN106589670A CN201611016598.9A CN201611016598A CN106589670A CN 106589670 A CN106589670 A CN 106589670A CN 201611016598 A CN201611016598 A CN 201611016598A CN 106589670 A CN106589670 A CN 106589670A
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China
Prior art keywords
hard pvc
color concentrate
parts
pvc color
pigment
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Pending
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CN201611016598.9A
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Chinese (zh)
Inventor
彭志远
薛燕
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CHENGDU FIRST CHEMICALS INDUSTRIAL Co Ltd
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CHENGDU FIRST CHEMICALS INDUSTRIAL Co Ltd
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Priority to CN201611016598.9A priority Critical patent/CN106589670A/en
Publication of CN106589670A publication Critical patent/CN106589670A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853Vinylacetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869Acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/04Compositions 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
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2310/00Masterbatches

Abstract

The invention discloses a hard PVC coloring master batch and belongs to the technical field of hard PVC processing. The coloring master batch comprises the following raw materials of, by weight, 16-25 parts of carriers, 14-80 parts of pigments, 0-60 parts of light calcium carbonate, 1-2 parts of stabilizers, 0-1 part of coupling agent and 0-5 parts of polyethylene wax. The carriers are one in EVA and EEA. The invention further provides a preparation method of the hard PVC coloring master batch. The coloring master batch has the advantages of being good in dispersity, high in pigment content concentration, good in electric insulation performance, heat resistance and weather resistance and free of discoloration.

Description

A kind of hard PVC color concentrate and preparation method thereof
Technical field
The present invention relates to a kind of hard PVC color concentrate and preparation method thereof, belongs to hard PVC processing technique field.
Background technology
PVC main components are polrvinyl chloride, the thermoplastic resin being polymerized under initiator effect by vinyl chloride, PVC Relative density 1.36, chlorinity 56~58%, PVC have bright in colour, corrosion-resistant, wearability, firm and durable, electrical insulating property good with And the advantages of fire retardant, self-extinguishment.Industrial PVC molecular weight typically in the range of 50,000~120,000, with larger polydispersion Property, the reduction of molecular weight with polymerisation temperature and increase.PVC is very hard, and without definite melting point, 80~85 DEG C start to soften, 130 DEG C of changes For viscoelastic state, 160~180 DEG C start to be changed into viscous state;There are preferable mechanical performance, tensile strength 60MPa or so, impact is strong 5~10kJ/m of degree2, there is excellent dielectric properties.
Igelite is divided into hard and soft two big class according to the number of added plasticizer.RPVC is moulded Material high mechanical strength, it is durable in use, for producing structural member, housing, toy, sheet material, tubing etc..Soft PVC quality is soft It is soft, for producing thin film, artificial leather, wallpaper, flexible pipe and cable conduct etc..
Now country's hard PVC product, most of by the way of " pigment+polyvinyl chloride resin+auxiliary agent " batch mixing, extrusion molding Production, multiple product, multiple color is mixed in a workshop, and dust from flying pollutes environment, damages workers ' health;Various pigment, friendship Fork pollution, product aberration are difficult to control to, and product quality defect is more;Product colour changing is time-consuming, laborious, cost is high etc., and PVC product is urgently The masterbatch for having maturation replaces toner.Another way is carried out after batch mixing by a certain percentage using color masterbatch and polyvinyl chloride resin, then is added Work is into product.
It is polyvinyl chloride resin sheet as carrier, such as Publication No. that PVC color masterbatches of the prior art is used CN104844959A、CN103694586A.The technical problem of presence:First, due to the melt viscosity of PVC it is inherently big, pigment Addition makes its viscosity bigger, and mobility declines, and so as to affect the dispersion of pigment, pigment concentration is higher, and fluidity of molten is poorer, face Material is more difficult dispersion, therefore does the color masterbatch of carrier using PVC, and the concentration of its pigment does not accomplish very high, it is impossible to meet actual making Use demand;Second, because the decomposition temperature of PVC melt temperatures and resin itself is very close to if adopting PVC for carrier, PVC melts Also along with the decomposition of PVC while change, after adding pigment, mobility can be deteriorated, and in an extruder the holdup time is elongated, be more easy to HCl is decomposited, makes pigment change colour, cause color masterbatch color unstable, affect product quality.
The content of the invention
Present invention seek to address that PVC color concentrates pigment concentration is not high in prior art, and PVC is used as masterbatch carrier band The problem of the pigment discoloration for coming, there is provided a kind of new hard PVC color concentrate, by reselecting to carrier, and to mother The particular design of material formula, the PVC color concentrates for obtaining have high concentration, high dispersive and heat-resisting, good weatherability without complexion changed Advantage.
In order to realize foregoing invention purpose, technical scheme is as follows:
A kind of hard PVC color concentrate, it is characterised in that:Including raw material in parts by mass:
16~25 parts of carrier;
14~80 parts of pigment;
0~60 part of precipitated calcium carbonate;
1~2 part of stabilizer;
0~1 part of coupling agent;
0~5 part of Tissuemat E;
The carrier is EVA(Ethylene-vinyl acetate copolymer)、EEA(Ethylene-ethyl acrylate copolymer)In one kind.
In order to be better achieved the present invention, the pigment is rutile titanium white lead, chrome yellow, molybdate orange, blue or green blue, forever solid At least one in purple, cadmium yellow, bronze red, channel black;Water content < 0.05% of the pigment.
Further, VA >=28% of the EVA, melt mass flow rate >=150g/10min.
The stabilizer be stearate, barium stearate, cadmium stearate, zinc stearate one or two.
Further, the zinc stearate of the preferred dry production of the stabilizer.
The coupling agent is silicone oil PMX-200.
It is a further object to provide the preparation method of the hard PVC color concentrate, comprises the following steps:
A. material is selected, selects satisfactory material as stated above.
B. batch mixing
Each raw material is mixed under room temperature, incorporation time is less than or equal to 20min;
C. extrude
The mixed material that step B is obtained is placed in extruder, melting extrusion is carried out, each warm area temperature of the extruder is 100 ~110 DEG C;
D. cooling, pelletize
After by the strand cooling extruded from extruder, pelletize obtains the hard PVC color concentrate.
Further, in step C, the screw thread of the extruder is soon the threaded block with dispersion impeller.
In step C, the gap between the threaded block and barrel reduces 30~60% compared with standard value.
In step D, the cooling is referred to and passes through strand from the water that temperature is 15~35 DEG C, temperature is too high, it is too low all Meeting fracture of wire, affects production efficiency.
Beneficial effects of the present invention:
(1)Compared with prior art, the present invention is used as vector resin by selecting polar material EVA or EEA, it is ensured that masterbatch Fluidity of molten is far longer than PVC, and after 70~80% pigment, filler is added, its mobility is still much larger than PVC, it is ensured that quality The little masterbatch of part PVC big with mass parts fully, uniformly mixes;Also, the carrier of polarity is good with the compatibility of PVC, with it is organic, Inorganic compound can be blended well, can bear the filling of high dose, such that it is able on the basis of the content for improving pigment On, while realizing high dispersive, meet the demand of user Geng Gao;In addition, the melting range of EVA and EVA is 87~92 DEG C, When color masterbatch prepares product as additive, melting extrusion can be carried out in not up to PVC decomposition temperatures, it is to avoid because of PVC Decompose and produce hydrogen chloride, cause the problem of product complexion changed.
Obtained color concentrate of the invention has following technical specification:
Melt mass flow rate(g/10min)≥40(The standards of GB/ 3682, condition D);
Dispersibility(Level) ≤3(GB/T 18251);
Thermostability(Level) ≥4(QB1648);
Resistance to migration(Level)≥4(QB1648);
Pigment content(%)14~80.
(2)In the present invention, the preferred rutile titanium white lead of pigment, chrome yellow, molybdate orange, blue or green blue, permanent violet, cadmium yellow, golden light At least one in red, channel black, the pigment can effectively delay the HCL of PVC to thermally decompose, and keep the electric insulating quality of PVC Can, and with good weatherability.
(3)In the present invention, stabilizer is stearate, barium stearate, cadmium stearate, zinc stearate one or two, Further preferred zinc stearate, zinc stearate agrees further to improve PVC heat stability, slow its HCL thermal decomposition of resistance.
(4)In the preparation method of the present invention, change the pattern of batch mixing after traditional heating, using room temperature batch mixing, prevent from heating up With because of storeroom frictional heating, cause pigment foxy, the mixing process of the present invention is capable of achieving preliminary using room temperature batch mixing Mixing, and substantial amounts of electric energy can be saved.
(5)In the preparation method of the present invention, in order to ensure more preferable pigment dispersion effect, traditional standard thread block is changed Into the threaded block with dispersion impeller, the uniformity that material mixes in an extruder more preferably, the obtaining in the carrier such as pigment, filler Preferably disperse.
(6)In the preparation method of the present invention, in order to further realize the dispersion effect of material, conventional extruder is reduced Gap 30~60% between threaded block and barrel, drastically increases the shearing force of extruder, and dispersion effect is more preferably.
Description of the drawings
Fig. 1 is the radial direction cross section structure diagram of the threaded block with dispersion impeller in extruder of the present invention;
Fig. 2 is the radial direction cross section structure diagram of threaded block of the prior art.
Wherein, 1- threaded blocks, 2- dispersion impellers.
Specific embodiment
The present invention is described in further detail with reference to embodiment, but embodiments of the present invention not limited to this.
Embodiment 1
A kind of hard PVC color concentrate, is made up of raw material in parts by mass:EVA16 parts, 10 parts of chrome yellow, molybdate red 10 Totally 1 part of part, 60 parts of precipitated calcium carbonate, barium stearate and cadmium stearate, 0.5 part of silicone oil, 4 parts of PE waxes.
Embodiment 2
A kind of hard PVC color concentrate, is made up of raw material in parts by mass:EVA25 parts, 30 parts of chrome yellow, molybdate red 10 Part, 35 parts of precipitated calcium carbonate, 2 parts of zinc stearate, 2 parts of PE waxes.
Embodiment 3
A kind of hard PVC color concentrate, by 25 parts of following matter parts of EVA, 20 parts of rutile titanium white lead, precipitated calcium carbonate 55 Part, 1 part of zinc stearate, 1 part of silicone oil.
Embodiment 4
A kind of hard PVC color concentrate, is made up of raw material in parts by mass:EVA20 parts, 80 parts of molybdate red, stearic acid 1 part of barium, 0.5 part of silicone oil.
Embodiment 5
A kind of hard PVC color concentrate, is made up of raw material in parts by mass:EVA20 parts, 16 parts of rutile titanium white lead, 8 parts of phthalocyanine blue, 1 part of permanent violet, 2 parts of zinc stearate, 5 parts of PE waxes.
Embodiment 6
The present embodiment is the preparation method of the color concentrate of embodiment 1 ~ 5:
A kind of preparation method of hard PVC color concentrate, comprises the following steps:
A. batch mixing
Each raw material is mixed under room temperature, incorporation time is 20min;
B. extrude
The mixed material that step A is obtained is placed in extruder, melting extrusion is carried out, each warm area temperature of the extruder is 100 ~110 DEG C;
C. cooling, pelletize
After by the strand cooling extruded from extruder, pelletize obtains the hard PVC color concentrate.
In the present embodiment, in step B, the threaded block of the extruder is the threaded block 1 with dispersion impeller 2, as shown in Figure 1.
In step B, the gap between the threaded block and barrel is 30% compared with primary standard gap shrinks.
In step C, the cooling is referred to and passes through strand from the water that temperature is 15~35 DEG C, temperature is too high, it is too low all Meeting fracture of wire, affects production efficiency.
Embodiment 7
A kind of hard PVC color concentrate, is made up of following raw material by weight:22 parts of EEA, 10 parts of chrome yellow, molybdate red 10 parts, 45 parts of precipitated calcium carbonate, 1 part of stabilizer zinc stearate, 0.5 part of silicone oil, 2 parts of PE waxes.
The preparation method of the color concentrate of the hard PVC color concentrate of the present embodiment is as follows:
A kind of preparation method of hard PVC color concentrate, comprises the following steps:
A. batch mixing
Each raw material is mixed under room temperature, incorporation time is 17min;
B. extrude
The mixed material that step A is obtained is placed in extruder, melting extrusion is carried out, each warm area temperature of the extruder is 100 ~110 DEG C;
C. cooling, pelletize
After by the strand cooling extruded from extruder, pelletize obtains the hard PVC color concentrate.
In the present embodiment, in step B, the threaded block of the extruder is the threaded block 1 with dispersion impeller 2, as shown in Figure 1.
In step B, the gap between the threaded block and barrel is compared with primary standard gap shrinks 60%.
In step C, the cooling is referred to and passes through strand from the water that temperature is 15~35 DEG C, temperature is too high, it is too low all Meeting fracture of wire, affects production efficiency.
Previous embodiment 1 ~ 5, color masterbatch index is as follows obtained in embodiment 7:
Explanation:In above table, matched group 1 is the color concentrate with PVC as vector resin, and its formula is:PVC50 parts, DOP (Plasticiser)50 parts, 30 parts of rutile titanium white lead, 5 parts of phthalocyanine blue, 1 part of permanent violet, 2.5 parts of zinc stearate, made using the present invention With equipment produced, but extruder temperature for PVC melt temperature(1800C or so).
Matched group 2 is that embodiments of the invention 1 are obtained using the preparation method of conventional PVC color concentrates, preparation method It is as follows:
In matched group 1, the masterbatch with PVC as carrier makes, and plasticiser, how many direct passes of plasticiser are must be added in formula It is the mobility of masterbatch, and then affects dispersibility, it is many that plasticiser adds, and the fluidity of molten of masterbatch is good, good dispersion, but can not For hard PVC coloring.Knowable to the data of table 1, its dispersibility does not reach the requirement of qualified products, and resistance to heat differential;In addition, control Using being produced using conventional batch mixer, extruder, the masterbatch dispersibility for obtaining equally does not reach requirement to group 2.The present invention From specific support material, it is ensured that carry out melting extrusion in not up to PVC decomposition temperatures, it is to avoid produce because PVC decomposes Raw hydrogen chloride, causes the problem of product complexion changed, and is equipped with the pigment of special ratios, stabilizer etc., further postpones, hinders slow The time of PVC decomposing Hs CL, and keep the good electrical insulation capability of product.
The above, is only presently preferred embodiments of the present invention, not does any pro forma restriction to the present invention, it is every according to According to any simple modification, equivalent variations that the technical spirit of the present invention is made to above example, the protection of the present invention is each fallen within Within the scope of.

Claims (10)

1. a kind of hard PVC color concentrate, it is characterised in that:Including following raw material by weight:
16~25 parts of carrier;
14~80 parts of pigment;
0~60 part of precipitated calcium carbonate;
1~2 part of stabilizer;
0~1 part of coupling agent;
0~5 part of Tissuemat E;
The carrier is the one kind in EVA, EEA.
2. a kind of hard PVC color concentrate as claimed in claim 1, it is characterised in that:The pigment be rutile titanium white lead, At least one in chrome yellow, molybdate orange, blue or green blue, permanent violet, cadmium yellow, bronze red, channel black;Water content < of the pigment 0.05%。
3. a kind of hard PVC color concentrate as claimed in claim 1, it is characterised in that:VA >=28% of the EVA, melt matter Amount flow rate >=150g/10min.
4. a kind of hard PVC color concentrate as claimed in claim 1, it is characterised in that:The stabilizer is stearate, firmly Fat acid barium, cadmium stearate, zinc stearate one or two.
5. a kind of hard PVC color concentrate as claimed in claim 4, it is characterised in that:The stabilizer is dry production Zinc stearate.
6. a kind of hard PVC color concentrate as claimed in claim 1, it is characterised in that:The coupling agent is silicone oil PMX- 200。
7. the preparation method of a kind of hard PVC color concentrate as described in any one of claim 1~6, it is characterised in that:Including Following steps:
A. material is selected
B. batch mixing
Each raw material is mixed under room temperature, incorporation time is less than or equal to 20min;
C. extrude
The mixed material that step B is obtained is placed in extruder, melting extrusion is carried out, each warm area temperature of the extruder is 100 ~110 DEG C;
D. cooling, pelletize
After by the strand cooling extruded from extruder, pelletize obtains the hard PVC color concentrate.
8. the preparation method of hard PVC color concentrate as claimed in claim 7, it is characterised in that:In step C, the extrusion The threaded block of machine is the threaded block with dispersion impeller.
9. the preparation method of hard PVC color concentrate as claimed in claim 8, it is characterised in that:In step C, the screw thread Gap between block and barrel reduces 30~60% compared with standard value.
10. the preparation method of hard PVC color concentrate as claimed in claim 7, it is characterised in that:In step D, the cooling Refer to and pass through strand from the water that temperature is 15~35 DEG C.
CN201611016598.9A 2016-11-18 2016-11-18 Hard PVC coloring master batch and preparation method thereof Pending CN106589670A (en)

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Application Number Priority Date Filing Date Title
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CN107118478A (en) * 2017-06-05 2017-09-01 合肥聪亨新型建材科技有限公司 A kind of novel tube and preparation method thereof
CN108314826A (en) * 2018-03-12 2018-07-24 宁波色母粒有限公司 The polyolefin cobalt blue master batch and preparation method thereof of resistance to strong acid corrosion
CN109096652A (en) * 2018-08-21 2018-12-28 山东寰宇线缆有限公司 A kind of applicable high-speed production automobile electric wire cable polyvinyl chloride Masterbatch and preparation method thereof
CN110540719A (en) * 2019-09-10 2019-12-06 成都菲斯特新材料有限公司 Coloring master batch for PVC electric power and electrician sleeve and preparation method thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107118478A (en) * 2017-06-05 2017-09-01 合肥聪亨新型建材科技有限公司 A kind of novel tube and preparation method thereof
CN108314826A (en) * 2018-03-12 2018-07-24 宁波色母粒有限公司 The polyolefin cobalt blue master batch and preparation method thereof of resistance to strong acid corrosion
CN109096652A (en) * 2018-08-21 2018-12-28 山东寰宇线缆有限公司 A kind of applicable high-speed production automobile electric wire cable polyvinyl chloride Masterbatch and preparation method thereof
CN110540719A (en) * 2019-09-10 2019-12-06 成都菲斯特新材料有限公司 Coloring master batch for PVC electric power and electrician sleeve and preparation method thereof

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