CN103351545B - Polyvinyl chloride composite materials of a kind of partially biodegradable and preparation method thereof - Google Patents

Polyvinyl chloride composite materials of a kind of partially biodegradable and preparation method thereof Download PDF

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Publication number
CN103351545B
CN103351545B CN201310226616.6A CN201310226616A CN103351545B CN 103351545 B CN103351545 B CN 103351545B CN 201310226616 A CN201310226616 A CN 201310226616A CN 103351545 B CN103351545 B CN 103351545B
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China
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polyvinyl chloride
district
leather
double
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CN103351545A (en
Inventor
段景宽
王亚娟
蒋岚
邵双喜
李亚
姚利辉
易疆川
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Guangdong Shunde Zhongce New Mstar Technology Ltd
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Ningbo University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/926—Flow or feed rate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Abstract

The invention discloses a kind of preparation method of polyvinyl chloride composite materials of partially biodegradable.The preparation method of matrix material gets leather fiber 100 parts by weight for (1), and leather modification agent 2 parts by weight carry out chemical modification in high-speed mixer, obtain the leather fiber of modification.(2) polyvinyl chloride 100 parts by weight are got, softening agent 30-60 weight part, thermo-stabilizer 2-4 weight part, polar waxes 2-5 weight part, stearic acid 1-4 weight part, modification leather fiber 10-30 weight part, after high-speed mixer mixes, obtains the polyvinyl chloride composite materials of partially biodegradable by the granulation of compound conical-double-helical rod forcing machine.The polyvinyl chloride composite materials mechanical property of the partially biodegradable that the present invention obtains is significantly improved than pure polyvinyl chloride, and the matrix material of preparation can be used for soft sheet material and row material.Preparation technology is simple, with low cost.

Description

Polyvinyl chloride composite materials of a kind of partially biodegradable and preparation method thereof
Technical field
The present invention relates to polymeric material field, be specifically related to polyvinyl chloride composite materials of a kind of partially biodegradable and preparation method thereof.
Background technology
Polyvinyl chloride is a kind of common plastics, especially soft PVC sheet material, electric wire, film etc. people daily in widely use.But pure soft PVC Mechanical Properties of Products, especially toughness and hardness are difficult to satisfy the demand.In order to improve and improve pure soft PVC products machinery performance, make soft PVC goods reach reasonably tough-firmly balance.Many scholars carry out modification to soft PVC.Be in soft PVC, add toughner and weighting agent to the means that soft PVC modification is main, such as patent CN101948595A adopts shoddy to carry out modification to polyvinyl chloride, and the mechanical property of polyvinyl chloride is significantly improved.Patent CN101402768A adopts acrylonitrile-isoprene-vinylbenzene and acrylate copolymer to carry out toughening modifying as impact modifying agent to polyvinyl chloride.Patent CN1439674A have employed inorganic nano-particle and has carried out activeness and quietness modification to polyvinyl chloride.Although these methods can improve the toughness of polyvinyl chloride, while toughness reinforcing, have also been changed the hardness of polyvinyl chloride.In addition, the polyvinyl chloride composite materials that these methods obtain does not have biological degradability.
In order to improve and improve the toughness of polyvinyl chloride composite materials, balanced polyvinyl chloride composite materials toughness and hardness, make the polyvinyl chloride composite materials obtained have biological degradability simultaneously.The present invention adopts has elasticity, and can the leather fiber of biological degradability as the plasticized modifier of polyvinyl chloride.This material is easy to get, and wide material sources are cheap.Leather fiber can derive from the tankage etc. of leatherware, waste leather goods, leatherware, just can use through simple mechanical disintegration.Therefore leather fiber is adopted both to improve the toughness of polyvinyl chloride as polyvinyl chloride toughening modifier, the price of polyvinyl chloride can be reduced again, waste and old leatherware can also be re-used simultaneously, decrease the waste of resource, the most important thing is the material that can obtain a kind of partially biodegradable, polyvinyl chloride can be made to be widely used in flexible article field, to expand the Application Areas of polyvinyl chloride.The present invention is in obtained polyvinyl chloride resin material, leather fiber is evenly distributed in body material polyvinyl chloride, strong mechanical property, impact property significantly improves, tensile strength does not obviously decline, and it is simple, with low cost that matrix material has partial biodegradability preparation method industry, is suitable for suitability for industrialized production.
Summary of the invention
Primary and foremost purpose of the present invention is that the shortcoming overcoming prior art is with not enough, and provide the matrix material that a kind of toughening polyvinyl chloride part biological is degraded, the mechanical property of this matrix material meets actual operation requirements, and cost performance is close to general polyvinyl chloride.
The polyvinyl chloride composite materials of partially biodegradable of the present invention is formed by following starting material and weight proportion mixture: polyvinyl chloride 100 parts, softening agent 30-60 part, thermo-stabilizer 2-4 part, polar waxes 2-5 part, stearic acid 1-4 part, leather fiber 10-30 part, leather modification agent 0.2-0.6 part.
Polyvinyl chloride of the present invention is selected from S-700, a kind of in S-1000 type resin or their mixture.
Softening agent of the present invention is selected from that butyl phthalate, octyl phthalate, trimellitic acid 1,2-anhydride, lemon are misery, one or several mixture in isooctyl citrate.
Thermo-stabilizer of the present invention is selected from the mixture of one or more in tribasic lead sulfate, dibasicity lead sulfate, barium stearate, calcium-zinc composite stabilizing agent, organotin stabilizer.
Polar polyethylene wax of the present invention is selected from the mixture of one or more in oxidized polyethlene wax, amide waxe, clorafin, maleic anhydride grafted polyethylene wax.
Leather fiber of the present invention mainly refers to the fibrous material obtained through mechanical disintegration by various animal's leather tankage, Leather Waste and leatherware.The order number of hide fiber is 10-500 order.
Leather modification agent of the present invention is selected from the mixture of one or more in glycidyl allyl ether, 3-glycydoxy methyldiethoxysilane, aminosilane.
The preparation method of the polyvinyl chloride composite materials of partially biodegradable of the present invention comprises the following steps:
(1) get leather fiber 100 parts by weight, leather modification agent 2 parts by weight carry out chemical modification in high-speed mixer, obtain the leather fiber of modification.
(2) polyvinyl chloride 100 parts by weight are got, softening agent 30-60 weight part, thermo-stabilizer 2-4 weight part, polar waxes 2-5 weight part, stearic acid 1-4 weight part, modification leather fiber 10-30 weight part, after high-speed mixer mixes, obtains the polyvinyl chloride composite materials of partially biodegradable by the granulation of compound conical-double-helical rod forcing machine.
Preparation method's processing condition of the polyvinyl chloride composite materials of partially biodegradable of the present invention comprise:
(1) in the high-speed mixer described in the working conditions that leather fiber carries out chemical modification be: temperature 70-95 DEG C, mixing machine rotating speed 500-800 rev/min, the time is 10-20 minute.
(2) working conditions polyvinyl chloride and other compositions mixed in high-speed mixer described in: temperature 80-110 DEG C, mixing machine rotating speed 800-1500 rev/min, the time is 5-10 minute.
(3) the conical-double-helical rod forcing machine granulation working conditions described in is: a district 110-120 DEG C, two district 120-140 DEG C, three district 140-160 DEG C, four district 160-170 DEG C, five district 170-175 DEG C, six district 170-175 DEG C, head 165-170 DEG C.Screw speed is 100-200 rev/min.Take recirculating air hot cut pellet.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
Testing method illustrates:
Tensile property examination is tested by GB/T1040-2006 standard, and draw speed is 5mm/min.
Tear strength is tested according to HG2-167-65 standard, and rate of bending is 2mm/min.
Shore hardness test is undertaken by ASTM D2240.
Compression permanent deformation is undertaken by GB/T7759-1996.
The chemical treatment of leather fiber
Comparative example 1:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 80 DEG C, mixing machine rotating speed controls at 600 revs/min, and churning time is discharging after 15 minutes, and numbering LF-0 is for subsequent use.
Embodiment 1:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 70 DEG C, mixing machine rotating speed controls at 600 revs/min, adds the 3-glycydoxy methyldiethoxysilane of 100g while stirring, and churning time is discharging after 15 minutes, and numbering GMA-1 is for subsequent use.
Embodiment 2:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 95 DEG C, mixing machine rotating speed controls at 600 revs/min, adds the 3-glycydoxy methyldiethoxysilane of 100g while stirring, and churning time is discharging after 15 minutes, and numbering GMA-2 is for subsequent use.
Embodiment 3:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 80 DEG C, mixing machine rotating speed controls at 600 revs/min, adds the 3-glycydoxy methyldiethoxysilane of 100g while stirring, and churning time is discharging after 15 minutes, and numbering GMA-3 is for subsequent use.
Embodiment 4:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 95 DEG C, mixing machine rotating speed controls, at 600 revs/min, to add the glycidyl allyl ether of 100g while stirring, and churning time is discharging after 15 minutes, and numbering AGE-1 is for subsequent use.
Embodiment 5:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 70 DEG C, mixing machine rotating speed controls, at 600 revs/min, to add the glycidyl allyl ether of 5g while stirring, and churning time is discharging after 15 minutes, and numbering AGE-2 is for subsequent use.
Embodiment 6:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 80 DEG C, mixing machine rotating speed controls, at 700 revs/min, to add the glycidyl allyl ether of 100g while stirring, and churning time is discharging after 15 minutes, and numbering AGE-3 is for subsequent use.
Embodiment 7:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 80 DEG C, mixing machine rotating speed controls at 800 revs/min, adds 3-glycydoxy methyldiethoxysilane and the 50g glycidyl allyl ether of 50g while stirring, and churning time is discharging after 15 minutes, numbering AGE+GMA-1, for subsequent use.
Embodiment 8:
The skin powder taking 5000g puts into high-speed mixer, starts to stir.After the temperature of high-speed mixer arrives 80 DEG C, mixing machine rotating speed controls, at 800 revs/min, to add the aminosilane of 100g while stirring, and churning time is discharging after 15 minutes, and numbering AG-1 is for subsequent use.
The preparation of the polyvinyl chloride composite materials of partially biodegradable
Comparative example 1:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Comparative example 2:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Comparative example 3:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, LF-0 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Comparative example 4:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, LF-0 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 1:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, GMA-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 2:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, GMA-2 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 3:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, GMA-3 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
AGE-1
Embodiment 4:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 5:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE-2 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 6:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE-3 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 6:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 7:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AG-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 8:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, GMA-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 9:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, GMA-2 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 10:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, GMA-3 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
AGE-1
Embodiment 11:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 12:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE-2 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 13:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE-3 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 14:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 15:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AG-1 hide fiber 1000g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 16:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 17:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AG-1 hide fiber 500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min
Embodiment 18:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 19:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 2500g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AG-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 20:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 3000g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 21:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 3000g, tribasic lead sulfate 75g, dibasicity lead sulfate 75g, oxidized polyethlene wax 150g, stearic acid 150g, AG-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 22:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 3000g, organotin stabilizer 150g, oxidized polyethlene wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 23:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 3000g, organotin stabilizer 150g, oxidized polyethlene wax 150g, stearic acid 150g, AG-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 24:
Take S-700 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 3000g, organotin stabilizer 150g, EBS wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 25:
Take S-1000 type polyvinyl chloride 5000g, dioctyl phthalate (DOP) 3000g, organotin stabilizer 150g, EBS wax 150g, stearic acid 150g, AG-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 26:
Take S-700 type polyvinyl chloride 5000g, dibutyl phthalate 3000g, organotin stabilizer 150g, EBS wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 27:
Take S-1000 type polyvinyl chloride 5000g, dibutyl phthalate 3000g, organotin stabilizer 150g, EBS wax 150g, stearic acid 150g, AG-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 150 revs/min.
Embodiment 28:
Take S-700 type polyvinyl chloride 5000g, dibutyl phthalate 3000g, organotin stabilizer 150g, EBS wax 150g, stearic acid 150g, AGE+GMA-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 130 DEG C, districts, three 150 DEG C, districts, four 165 DEG C, districts, five 175 DEG C, districts, six 175 DEG C, districts, head 170 DEG C.Screw speed is 200 revs/min.
Embodiment 29:
Take S-700 type polyvinyl chloride 5000g, dibutyl phthalate 3000g, organotin stabilizer 150g, EBS wax 150g, stearic acid 150g, AG-1 hide fiber 1500g, the high-speed mixing 5 minutes of 80 DEG C, at conical-double-helical rod forcing machine recirculating air hot cut pellet after discharging.Conical-double-helical rod forcing machine granulation working conditions is: 110 DEG C, a district, two 135 DEG C, districts, three 155 DEG C, districts, four 170 DEG C, districts, five 180 DEG C, districts, six 170 DEG C, districts, head 165 DEG C.Screw speed is 150 revs/min.
The made material property of embodiment 1-29 and comparative example 1-4 is in table 1.
The made material property of table 1 embodiment 1-29 and comparative example 1-4
As can be seen from Table 1, the performance of the embodiment test of application technical solution of the present invention is significantly improved in toughness relative to comparative example, and other performance does not all have larger decline.

Claims (2)

1. the polyvinyl chloride composite materials of a partially biodegradable, it is characterized in that: matrix material is formed by following starting material and weight proportion mixture: polyvinyl chloride 100 parts, softening agent 30-60 part, thermo-stabilizer 2-4 part, polar waxes 2-5 part, stearic acid 1-4 part, leather fiber 10-30 part, leather modification agent 0.2-0.6 part;
Wherein, described polyvinyl chloride is selected from S-700, a kind of in S-1000 type resin or their mixture;
Wherein, described softening agent is selected from one or several the mixture in butyl phthalate, octyl phthalate, trimellitic acid 1,2-anhydride, citric acid monooctyl ester, isooctyl citrate;
Wherein, described thermo-stabilizer is selected from the mixture of one or more in tribasic lead sulfate, dibasicity lead sulfate, barium stearate, calcium-zinc composite stabilizing agent, organotin stabilizer;
Wherein, described polar waxes is selected from the mixture of one or more in oxidized polyethlene wax, amide waxe, clorafin, maleic anhydride grafted polyethylene wax;
Wherein, described leather fiber mainly refers to the fibrous material obtained through mechanical disintegration by various animal's leather tankage, Leather Waste and leatherware, and the order number of hide fiber is 10-500 order;
Wherein, described leather modification agent is selected from the mixture of one or more in glycidyl allyl ether, 3-glycydoxy methyldiethoxysilane, aminosilane.
2. prepare a method for the polyvinyl chloride composite materials of partially biodegradable according to claim 1, it is characterized in that comprising the following steps:
(1) leather fiber 100 parts by weight are got, leather modification agent 2 parts by weight carry out chemical modification in high-speed mixer, and working conditions is: temperature 70-95 DEG C, mixing machine rotating speed 500-800 rev/min, time is 10-20 minute, obtains modification leather fiber;
(2) polyvinyl chloride 100 parts by weight are got, softening agent 30-60 weight part, thermo-stabilizer 2-4 weight part, polar waxes 2-5 weight part, stearic acid 1-4 weight part, modification leather fiber 10-30 weight part, mix at high-speed mixer, working conditions: temperature 80-110 DEG C, mixing machine rotating speed 800-1500 rev/min, the time is 5-10 minute;
(3) the compound conical-double-helical rod forcing machine granulation will mixed, working conditions is: a district 110-120 DEG C, two district 120-140 DEG C, three district 140-160 DEG C, four district 160-170 DEG C, five district 170-175 DEG C, six district 170-175 DEG C, head 165-170 DEG C; Screw speed is 100-200 rev/min; Take recirculating air hot cut pellet; Obtain the polyvinyl chloride composite materials of partially biodegradable.
CN201310226616.6A 2013-05-30 2013-05-30 Polyvinyl chloride composite materials of a kind of partially biodegradable and preparation method thereof Expired - Fee Related CN103351545B (en)

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CN101775168A (en) * 2010-01-12 2010-07-14 浙江理工大学 Collagen-modified biodegradable plastic and preparation method thereof
CN102002180A (en) * 2010-11-03 2011-04-06 宁波工程学院 Method for preparing compatible hide powder/polyethylene mixture
CN102115587A (en) * 2010-12-30 2011-07-06 李兵 Polymer section and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN101775168A (en) * 2010-01-12 2010-07-14 浙江理工大学 Collagen-modified biodegradable plastic and preparation method thereof
CN102002180A (en) * 2010-11-03 2011-04-06 宁波工程学院 Method for preparing compatible hide powder/polyethylene mixture
CN102115587A (en) * 2010-12-30 2011-07-06 李兵 Polymer section and preparation method thereof

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Inventor after: Wu Hanwen

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