CN1640919A - Starchlike biological degradatable plastic mother material and its preparation method - Google Patents

Starchlike biological degradatable plastic mother material and its preparation method Download PDF

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Publication number
CN1640919A
CN1640919A CNA2004100614160A CN200410061416A CN1640919A CN 1640919 A CN1640919 A CN 1640919A CN A2004100614160 A CNA2004100614160 A CN A2004100614160A CN 200410061416 A CN200410061416 A CN 200410061416A CN 1640919 A CN1640919 A CN 1640919A
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starch
biodegradable plastic
master batch
plastic master
agent
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CN1326928C (en
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陈明忠
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SUZHOU HANFENG NEW MATERIAL CO., LTD.
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陈明忠
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Priority to CNB2004100614160A priority Critical patent/CN1326928C/en
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Priority to PCT/CN2005/001884 priority patent/WO2006066478A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/02—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to polysaccharides
    • 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
    • C08K2201/018—Additives for biodegradable polymeric composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Abstract

The present invention is biodegradable plastic mother material and its preparation process, and has the features of simple production process, low cost, etc. The biodegradable plastic mother material is prepared with material including starch, starch grafting modifier, bonding resin, bonding resin grafting modifier, bonding resin grafting initiator, lubricating plasticizer, stabilizer, dispersant and degradation assistant. The preparation process includes starch grafting modification, bonding resin grafting modification and other steps. The biodegradable plastic mother material has excellent biocompatibility, high starch content and high biodegrading performance.

Description

Starch based biodegradable plastic master batch and preparation method thereof
Technical field:
The present invention relates to a kind of starch based biodegradable plastic master batch and preparation method thereof.
Background technology:
At present, disclosed starch based biodegradable plastic master batch is as 99100726.3 00119372.4 patents such as 01134820.8 for another example and for example, described preparation method needs starch is carried out homogenate dipping, liquid dehydration, pulpous state refinement, the high mixed modification of coupling, processing such as double-screw extruding pelletizing, and the required equipment investment is big, operation is many, production cycle is long, but also only is that the modification of starch is handled, so that the starch addition is few, sanitation performance is poor, the cost height.
Summary of the invention:
The invention solves that prior art investment is big, operation is many, the production cycle is long, sanitation performance is poor, defect of high cost, and starch based biodegradable plastic master batch that a kind of production technique is simple, cost is low, sanitation performance is good and preparation method thereof is provided.
Technical solution of the present invention is as follows:
1, starch based biodegradable plastic master batch
It comprises following component and ratio of weight and number: 100 parts of starch, 0.5～3 part of grafting modified of starch agent, 30～300 parts of tacky resins, 0.5～4 part of tacky resin graft modification agent, 0.1～1 part of tacky resin graft reaction initiator, 3～30 parts in lubricated softening agent, 1～3 part of stablizer, 1～3 part of dispersion agent helps 0～2 part of degradation agents.
2, above-mentioned starch based method for preparing biodegradable plastic master batch may further comprise the steps:
(1) starch conversion grafting:
1. starch refinement:, stand-by with primary starch dispersion and fining.
2. starch conversion grafting: in refinement starch, add lubricated softening agent, highly then stir, heat up, gradation adds the grafting modified of starch agent of respective numbers, highly again stir, heat up, add the stablizer of respective numbers, high again stirring, add the dispersion agent of respective numbers and help degradation agents, high again stir to mixing of materials even; Stir the cooling back modify and graft starch, pack stand-by.
(2) tacky resin graft modification:
1. in the tacky resin material, add the tacky resin graft modification agent of respective numbers, the tacky resin graft reaction initiator of respective numbers, after stirring, stretching and granulation or the fervent granulation of die face tacky resin graft modification material, pack stand-by thereafter.
2. owing to polycaprolactone, poly(lactic acid), poly-glycollide, polylactide, polyhydroxyalkanoate, ethylene/acrylic acid copolymer, ethylene/ethyl acrylate multipolymer, ethylene/vinyl acetate multipolymer have been good compatilizer, need not carry out graft modification again.
(4) starch based biodegradable plastic master batch preparation:
In modify and graft starch, one or more in adding tacky resin graft modification material or the compatilizer stir, and the starch based biodegradable plastic master batch is promptly made in the fervent granulation of stretching and granulation or die face.
The present invention is owing to all carry out graft modification to starch and tacky resin, and its consistency is splendid for this reason, produces the structure that you are among us and we are among you, thereby realizes the material of high starch, high biological degradability.
Embodiment:
1, starch based biodegradable plastic master batch, its composition comprises following component and ratio of weight and number: 100 parts of refinement starch, 0.5～3 part of grafting modified of starch agent, 30～300 parts of tacky resins, 0.5～4 part of tacky resin graft modification agent, 0.1～1 part of tacky resin graft reaction initiator, 3～30 parts in lubricated softening agent, 1～3 part of stablizer, 1～3 part of dispersion agent helps 0～2 part of degradation agents.
Described refinement starch is to be become in the plant amylums such as 1200～2000 purpose W-Gums, tapioca (flour), horse mountain range sweet potato starch, wheat starch, sweet potato starch one or more by air-flow vortex pulverizing mill powder is pure.
Described grafting modified of starch agent is wherein one or more such as titanate coupling agent, aluminate coupling agent, silane coupling agent.
Described tacky resin is wherein one or more such as polycaprolactone, poly(lactic acid), poly-glycollide, polylactide, polyhydroxyalkanoate, ethylene/acrylic acid copolymer, ethylene/ethyl acrylate multipolymer, ethylene/vinyl acetate multipolymer, high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene, polypropylene, polystyrene.
Described tacky resin graft modification agent is wherein one or more such as maleic anhydride, diacetyl oxide, Succinic anhydried, methacrylic anhydride.
Described tacky resin graft reaction initiator is wherein one or more such as dicumyl peroxide (DCP) or hydrogen phosphide cumene (CHP).
Described lubricated softening agent is white oil, naphthenic oil, glycerine, sorbyl alcohol.Wherein one or more such as ethylene glycol propylene glycol.
Described stablizer is wherein one or more such as hard ester acid, sodium stearate, calcium stearate, barium stearate.
Described dispersion agent is compound wherein one or more such as cured of compound cured, the polypropylene of liquid paraffin wax, oxidic polyethylene, polyethylene.
The described degradation agents that helps is one or more of controlled degradation additive, photodegradable aid.
2, preparation method;
Above-mentioned starch based method for preparing biodegradable plastic master batch may further comprise the steps:
(1) starch conversion grafting:
1. starch refinement: start ACM-60 type air-flow vortex pulverizing mill, the primary starch of about 100 orders is slowly dropped in the ACM-60 type air-flow vortex pulverizing mill, regulate refinement starch discharging classification rotating speed to the refinement starch particle diameter of discharging at about 1200～2000 orders of 10um～6um, pack stand-by thereafter.
2. starch conversion grafting: start the high-speed mixer running of 500/1000 high cold mixer group, 100 weight part refinement starch are dropped in the high-speed mixer, stir temperature at height and rise to the lubricated softening agent that adds 3～30 parts after about 80 ℃, highly then stir that about temperature rises to 100 ℃ after five minutes, three each interval addings in two minutes of branch respective numbers is 0.5～3 part grafting modified of starch agent, highly again stir five minutes about temperature and rise to 120 ℃, the stablizer that adds 1～3 part, high again stirring three minutes adds the degradation agents that helps of 1～3 part of dispersion agent and 0～2 part.High again stir one minute approximately in the pot mixing of materials evenly put in the cold mixed pot cooling and stirring take the dish out of the pot after about 60 ℃ modify and graft starch, pack stand-by.
(2) tacky resin graft modification:
In 100 parts of tacky resin material; add 0.5～4 part of tacky resin graft modification agent, 0.1～1 part of tacky resin graft reaction initiator, after the mixing and stirring, through stretching and granulation or the fervent granulation of die face; tacky resin graft modification material, pack stand-by thereafter.But polycaprolactone, poly(lactic acid), poly-glycollide, polylactide, polyhydroxyalkanoate, ethylene/acrylic acid copolymer, ethylene/ethyl acrylate multipolymer, ethylene/vinyl acetate multipolymer have been good compatilizer, need not carry out graft modification again.
(3) starch based biodegradable plastic master batch preparation:
One or more that get that 100 parts of modify and graft starch add 30～300 parts of tacky resin graft modification material or phase solvent stir, and pour in the twin screw extruder and promptly make the starch based biodegradable plastic master batch in certain temperature, extrusion pressure and the granulation of vacuumizing and exhausting bottom brace or the fervent granulation of die face.What wherein only make with compatilizer is the biological degradation plastics masterbatch.
Embodiment 1:
1. start ACM-60 type air-flow vortex pulverizing mill, the primary W-Gum of about 100 orders of 1000kg is slowly dropped in the ACM-60 type air-flow vortex pulverizing mill, regulate refinement starch particle diameter 10um below about 1200 orders of refinement starch discharging classification rotating speed to discharging.2. start the high-speed mixer running of 500/1000 high cold mixer group, 130kg refinement starch is dropped in the high-speed mixer, stir at height and to add white oil 20kg after temperature rises to about 80 ℃, highly then stir that about temperature rises to 100 ℃ after five minutes, dividing three times, each to add respective numbers in two minutes at interval be the CT-114 type titanate coupling agent of 1.8kg, highly again stirs five minutes about temperature and rise to 120 ℃, adding 2kg stearic acid, high again stirring three minutes adds the cured and 0.13kg low thermal oxidation degradation agents of 3kg polypropylene.High again stir one minute approximately in the pot mixing of materials put into evenly that cooling and stirring takes the dish out of the pot in the cold mixed pot after about 60 ℃.3. the 100kg polypropylene granules is poured in the agitator kettle, adding 3kg maleic anhydride, 0.1kg dicumyl peroxide are poured in the twin screw extruder hopper after stirring, and regulate and control each technological temperature (is example by the double gas granulation of TSE75 type twin screw unit) and are:
1 group 190 ℃～210 ℃ 2 groups 195 ℃～220 ℃ 3 groups 200 ℃～230 ℃ 4 groups 210 ℃～240 ℃ 5 groups 220 ℃～250 ℃
6 groups 230 ℃～260 ℃ 240 ℃～260 ℃ of drapings 240 ℃～260 ℃ at elbow 240 ℃～260 ℃ of die heads 240 ℃～270 ℃ of melt actual temperatures
After being heated to design temperature, be incubated 30 minutes, open main frame, slowly speed governing to 200 changes～450 changes.After treating that twin screw runs well, regulation and control metering feeding twin screw rotating speed notices that the main control system electric current is between 180A～220A between 6～20, melt pressure is controlled between 4～9, when treating the die orifice discharging, regulate pelletizing speed to suitable granular, graft polypropylene.4. get 100kg modify and graft starch and add the 60kg graft polypropylene and stir, pour in the hopper of the double gas forcing machine of twin screw, regulate and control each technological temperature (is example by the double gas granulation of TSE75 type twin screw unit) and be:
1 group 120 ℃～145 ℃ 2 groups 125 ℃～150 ℃ 3 groups 130 ℃～155 ℃ 4 groups 135 ℃～160 ℃ 5 groups 140 ℃～165 ℃
6 groups 140 ℃～165 ℃ 140 ℃～165 ℃ of drapings 140 ℃～165 ℃ at elbow 140 ℃～165 ℃ of die heads 155 ℃～165 ℃ of melt actual temperatures
After being heated to design temperature, be incubated 15 minutes to 30 minutes, open main frame, slowly speed governing to 200 changes～450 changes.After treating that twin screw runs well, adjust temperature to 120 ℃～150 ℃, note the main control system electric current between 180A～220A, melt pressure is controlled between 4～9, opens vacuum pumping hardware, and control vacuum tightness is about 0.06～0.09Mpa.Regulation and control metering feeding twin screw rotating speed is between 6～20, and when treating the die orifice discharging, the pelletizing speed of regulating stretching and granulation to the suitable granular starch content of promptly making is 50% PP level starch based biodegradable plastic master batch.This product is applicable to product materials such as sheet material, curtain coating plastic uptake, food and drink tool, artwork packing, injection-molded item.
Embodiment 2:
(1) starts ACM-60 type air-flow vortex pulverizing mill, the primary W-Gum of about 100 orders of 1000kg is slowly dropped in the ACM-60 type air-flow vortex pulverizing mill, regulate refinement starch particle diameter 6.5um below about 2000 orders of refinement starch discharging classification rotating speed to discharging.
(2) the high-speed mixer running of startup 500/1000 high cold mixer group, 150kg refinement starch is dropped in the high-speed mixer, stir at height and to add glycerine 20kg after temperature rises to about 60 ℃, highly then stir that about temperature rises to 90 ℃ after five minutes, dividing three times, each to add respective numbers in two minutes at interval be the DH-411 type aluminate coupling agent of 1.8kg, highly again stirs five minutes about temperature and rise to 120 ℃, adding 2kg sodium stearate, high again stirring three minutes adds the 3kg Ployethylene Wax.High again stir one minute approximately in the pot mixing of materials put into evenly that cooling and stirring takes the dish out of the pot in the cold mixed pot after about 60 ℃.
(3) get that 100kg modify and graft starch adds 20kg ethylene/acrylic acid copolymer (EAA), the 50kg polycaprolactone stirs, pour in the hopper of the double gas forcing machine of twin screw, regulate and control each technological temperature (is example by the double gas granulation of TSE75 type twin screw unit) and be:
1 group 100 ℃～125 ℃ 2 groups 105 ℃～130 ℃ 3 groups 110 ℃～135 ℃ 4 groups 115 ℃～140 ℃ 5 groups 120 ℃～145 ℃
6 groups 120 ℃～145 ℃ 120 ℃～145 ℃ of drapings 120 ℃～145 ℃ at elbow 120 ℃～145 ℃ of die heads 125 ℃～145 ℃ of melt actual temperatures
After being heated to design temperature, be incubated 15 minutes to 30 minutes, open main frame, slowly speed governing to 200 changes～450 changes.After treating that twin screw runs well, adjust temperature to 100 ℃～140 ℃, note the main control system electric current between 180A～220A, melt pressure is controlled between 4～9, opens vacuum pumping hardware, and control vacuum tightness is about 0.06～0.09Mpa.Regulation and control metering feeding twin screw rotating speed is between 6～20, and when treating the die orifice discharging, regulating the fervent pelletizing speed of die face to the suitable granular starch content of promptly making is 50% starch based biological degradation plastics masterbatch.This product is applicable to product materials such as the various types of films goods that require complete biodegradable, food and drink tool articles for use, technology packaged product.
Embodiment 3:
(1) starts ACM-60 type air-flow vortex pulverizing mill, the primary W-Gum of about 100 orders of 1000kg is slowly dropped in the ACM-60 type air-flow vortex pulverizing mill, regulate refinement starch particle diameter 8um below about 1600 orders of refinement starch discharging classification rotating speed to discharging.
(2) the high-speed mixer running of startup 500/1000 high cold mixer group, 100kg refinement starch is dropped in the high-speed mixer, stir at height and to add glycerine 15kg after temperature rises to about 70 ℃, highly then stir that about temperature rises to 90 ℃ after five minutes, dividing three times, each to add respective numbers in two minutes at interval be the CT-114 type titanate coupling agent of 1.2kg, highly again stirs five minutes about temperature and rise to 120 ℃, adding 1.5kg stearic acid, high again stirring three minutes adds 2kg Ployethylene Wax and 0.1kg low thermal oxidation degradation agents.High again stir one minute approximately in the pot mixing of materials put into evenly that cooling and stirring takes the dish out of the pot in the cold mixed pot after about 60 ℃.
(3) 120kg linear low density polyethylene pellet is poured in the agitator kettle; adding 4kg Succinic anhydried, 0.1kg hydrogen phosphide cumene are poured in the twin screw extruder hopper after stirring, and regulate and control each technological temperature (is example by the double gas granulation of TSE75 type twin screw unit) and are:
1 group 140 ℃～160 ℃ 2 groups 145 ℃～160 ℃ 3 groups 145 ℃～165 ℃ 4 groups 145 ℃～165 ℃ 5 groups 150 ℃～170 ℃
6 groups 155 ℃～170 ℃ 155 ℃～170 ℃ of drapings 155 ℃～170 ℃ at elbow 155 ℃～170 ℃ of die heads 150 ℃～170 ℃ of melt actual temperatures
After being heated to design temperature, be incubated 30 minutes, open main frame, slowly speed governing to 200 changes～450 changes.After treating that twin screw runs well, regulation and control metering feeding twin screw rotating speed notices that the main control system electric current is between 180A～220A between 6～20, melt pressure is controlled between 4～9, when treating the die orifice discharging, regulate the fervent pelletizing speed of die face to suitable granular, grafted polyethylene.4. get that 100kg modify and graft starch adds the 20kg grafted polyethylene, 10kg ethylene/ethyl acrylate multipolymer (EEA) stirs; pour in the hopper of the double gas forcing machine of twin screw, regulate and control each technological temperature (is example by the double gas granulation of TSE75 type twin screw unit) and be:
1 group 115 ℃～140 ℃ 2 groups 120 ℃～145 ℃ 3 groups 125 ℃～150 ℃ 4 groups 130 ℃～155 ℃ 5 groups 135 ℃～160 ℃
6 groups 135 ℃～160 ℃ 135 ℃～160 ℃ of drapings 135 ℃～160 ℃ at elbow 135 ℃～160 ℃ of die heads 145 ℃～155 ℃ of melt actual temperatures
After being heated to design temperature, be incubated 30 minutes, open main frame, slowly speed governing to 200 changes～450 changes.After treating that twin screw runs well, regulation and control metering feeding twin screw rotating speed is noted the main control system electric current between 180A～220A between 6～20, and melt pressure is controlled between 4～9, opens vacuum pumping hardware, and control vacuum tightness is about 0.06～0.09Mpa.Regulation and control metering feeding twin screw rotating speed is between 6～20, and when treating the die orifice discharging, regulating the fervent pelletizing speed of die face to the suitable granular starch content of promptly making is 65% PE level starch based biodegradable plastic master batch.This product is applicable to materials such as various types of films goods, hollow piece, sheet material, injection-molded item, Blister product.

Claims (16)

1 one kinds of starch based biodegradable plastic master batch, it is characterized in that: it comprises following component and ratio of weight and number: 100 parts of starch, 0.5～3 part of grafting modified of starch agent, 30～300 parts of tacky resins, 3～30 parts in lubricated softening agent, 1～3 part of stablizer, 1～3 part of dispersion agent helps 0～2 part of degradation agents.
2, starch based biodegradable plastic master batch according to claim 1 is characterized in that: it also comprises 0.5～4 part of tacky resin graft modification agent, 0.1～1 part of tacky resin graft reaction initiator.
3, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described starch is for being become in 1200～2000 purpose W-Gums or tapioca (flour) or horse mountain range sweet potato starch or the plant amylums such as wheat starch or sweet potato starch one or more by powder is pure.
4, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described grafting modified of starch agent is wherein one or more of titanate coupling agent or aluminate coupling agent or silane coupling agent etc.
5, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described tacky resin is one or more in polycaprolactone or poly(lactic acid) or poly-glycollide or polylactide or polyhydroxyalkanoate or ethylene/acrylic acid copolymer or ethylene/ethyl acrylate multipolymer or ethylene/vinyl acetate multipolymer or high density polyethylene(HDPE) or new LDPE (film grade) or linear low density polyethylene or polypropylene or the polystyrene.
6, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described tacky resin graft modification agent is one or more in maleic anhydride or diacetyl oxide or Succinic anhydried or the methacrylic anhydride.
7, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described tacky resin graft reaction initiator is a kind of in dicumyl peroxide or the hydrogen phosphide cumene or two kinds.
8, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described lubricated softening agent is one or more in white oil or naphthenic oil or glycerine or sorbyl alcohol or the ethylene glycol propylene glycol.
9, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described stablizer is one or more in hard ester acid or sodium stearate or the calcium stearate.
10, starch based biodegradable plastic master batch according to claim 2 is characterized in that: described dispersion agent is compound in cured one or more of the compound cured or polypropylene of liquid paraffin wax or oxidic polyethylene or polyethylene.
11, starch based biodegradable plastic master batch according to claim 1 is characterized in that: the described degradation agents that helps is one or more of controlled degradation additive or photodegradable aid.
12, according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 described starch based method for preparing biodegradable plastic master batch, it is characterized in that:
It may further comprise the steps:
(1) starch conversion grafting:
1. starch refinement:, stand-by with primary starch dispersion and fining;
2. starch conversion grafting: in refinement starch, add lubricated softening agent, highly then stir, heat up, gradation adds the grafting modified of starch agent of respective numbers, highly again stir, heat up, add the stablizer of respective numbers, high again stirring, add the dispersion agent of respective numbers and help degradation agents, high again stir to mixing of materials even; Stir the cooling back modify and graft starch, pack stand-by;
(2) tacky resin graft modification:
1. in the tacky resin material, add the tacky resin graft modification agent of respective numbers, the tacky resin graft reaction initiator of respective numbers, after stirring, stretching and granulation or the fervent granulation of die face tacky resin graft modification material, pack stand-by thereafter;
2. owing to polycaprolactone, poly(lactic acid), poly-glycollide, polylactide, polyhydroxyalkanoate, ethylene/acrylic acid copolymer, ethylene/ethyl acrylate multipolymer, ethylene/vinyl acetate multipolymer have been good compatilizer, need not carry out graft modification again;
(3) starch based biodegradable plastic master batch preparation:
In modify and graft starch, one or more in adding tacky resin graft modification material or the compatilizer stir the fervent granulation of stretching and granulation or die face.
13, starch based method for preparing biodegradable plastic master batch according to claim 12 is characterized in that: about 100 order refinement starch particle diameters are refined to about 1200～2000 orders of 10um～6um.
14, starch based method for preparing biodegradable plastic master batch according to claim 12, it is characterized in that: the concrete technology of described starch conversion grafted is: 100 weight part refinement starch are dropped in the high-speed mixer, stir temperature at height and rise to the lubricated softening agent that adds 3～30 parts after about 80 ℃, highly then stir that about temperature rises to 100 ℃ after five minutes, three each interval addings in two minutes of branch respective numbers is 0.5～3 part grafting modified of starch agent, highly again stir five minutes about temperature and rise to 120 ℃, the stablizer that adds 1～3 part, high again stirring three minutes adds the degradation agents that helps of 1～3 part of dispersion agent and 0～2 part; High again stir one minute approximately in the pot mixing of materials evenly put in the cold mixed pot cooling and stirring take the dish out of the pot after about 60 ℃ modify and graft starch.
15, starch based method for preparing biodegradable plastic master batch according to claim 12; it is characterized in that: the concrete technology of described tacky resin graft modification is: in 100 parts of tacky resin material; add 0.5～4 part of tacky resin graft modification agent, 0.1～1 part of tacky resin graft reaction initiator; after the mixing and stirring; through stretching and granulation or the fervent granulation of die face; tacky resin graft modification material, pack stand-by thereafter.
16, starch based method for preparing biodegradable plastic master batch according to claim 12, it is characterized in that: the concrete technology of described starch based biodegradable plastic master batch preparation is: one or more that get that 100 parts of modify and graft starch add 30～300 parts of tacky resin graft modification material or phase solvent stir, and pour in the twin screw extruder and promptly make the starch based biodegradable plastic master batch in certain temperature, extrusion pressure and the granulation of vacuumizing and exhausting bottom brace or the fervent granulation of die face; What wherein only make with compatilizer is the biological degradation plastics masterbatch.
CNB2004100614160A 2004-12-20 2004-12-20 Starchlike biological degradatable plastic mother material and its preparation method Expired - Fee Related CN1326928C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CNB2004100614160A CN1326928C (en) 2004-12-20 2004-12-20 Starchlike biological degradatable plastic mother material and its preparation method
PCT/CN2005/001884 WO2006066478A1 (en) 2004-12-20 2005-11-09 A biodegradable starch-based master batch and a method for preparing the same

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CN101831097A (en) * 2010-04-09 2010-09-15 常州百利基生物材料科技有限公司 Biodegradable mulching film
CN101942114A (en) * 2010-09-03 2011-01-12 北京新华联生物材料有限公司 Biodegradable amylum colophony for injection molding and preparation method and products thereof
CN102627935A (en) * 2012-03-23 2012-08-08 长沙乐远化工科技有限公司 Biodegradable aqueous emulsion-type polylactic acid adhesive and its preparation method
CN103059146A (en) * 2013-02-05 2013-04-24 湘潭大学 Starch surface treatment process
CN103937036A (en) * 2014-04-23 2014-07-23 苏州羽帆新材料科技有限公司 Environment-friendly plastic containing modified starch
CN103992515A (en) * 2014-04-30 2014-08-20 安徽省宁国市明浩包装材料有限公司 High-transmittance degradable agricultural film
CN104151626A (en) * 2014-07-17 2014-11-19 安徽巢湖南方膜业有限责任公司 Phosphate starch-polyethylene composite plastic film and preparation method thereof
CN104292636A (en) * 2014-09-30 2015-01-21 苏州博利迈新材料科技有限公司 Photo-and-biological double degradation composite material for lunch box and preparation method thereof
CN104441542A (en) * 2014-11-18 2015-03-25 东莞市方中运动制品有限公司 Drawing process and application of starch degradable plastics
CN104448398A (en) * 2014-11-18 2015-03-25 东莞市方中运动制品有限公司 Cassava degradable plastic as well as production process and production equipment thereof
CN104861210A (en) * 2015-04-30 2015-08-26 亿帆鑫富药业股份有限公司 Starch-base fully biodegradable resin with steady hydrophobic property and preparation method thereof
CN103992515B (en) * 2014-04-30 2016-11-30 刘孟香 A kind of high light transmittance degradable agricultural film
CN106243404A (en) * 2016-08-30 2016-12-21 安徽锦鸿环保科技有限公司 Starch degradable thin film of caprolactone grafting that a kind of transparency is good and preparation method thereof
CN106243403A (en) * 2016-08-30 2016-12-21 安徽锦鸿环保科技有限公司 A kind of tear-resistant starch degradable thin film of caprolactone grafting and preparation method thereof
CN107814955A (en) * 2017-11-14 2018-03-20 成都新柯力化工科技有限公司 A kind of water resistant starch base biodegradation plastic matrix and preparation method thereof
CN109897327A (en) * 2019-03-06 2019-06-18 盐城市涌泉排水板有限公司 A kind of biodegradable drain bar and its preparation process
CN111019601A (en) * 2019-12-26 2020-04-17 成都新柯力化工科技有限公司 Low-cost biodegradable hot melt adhesive special for paper packaging and preparation method thereof
CN114133629A (en) * 2021-12-25 2022-03-04 汕头市天悦科技创新研究院有限公司 Modified active starch degradation plastic master batch and preparation method thereof

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CN117603402A (en) * 2024-01-19 2024-02-27 寿光金远东变性淀粉有限公司 Composite modified starch for biodegradable plastic and preparation method thereof

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US6090884A (en) * 1998-05-07 2000-07-18 S. C. Johnson Commercial Markets, Inc. Starch degradation/graft polymerization composition, process, and uses thereof
CN1081203C (en) * 1999-02-11 2002-03-20 天津丹海股份有限公司 Preparation of mother material for biodegradable plastics
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CN1267487C (en) * 2004-08-23 2006-08-02 成都新柯力化工科技有限公司 Biodegradation starch resin masterbatch

Cited By (24)

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Publication number Priority date Publication date Assignee Title
CN101831097A (en) * 2010-04-09 2010-09-15 常州百利基生物材料科技有限公司 Biodegradable mulching film
CN101942114A (en) * 2010-09-03 2011-01-12 北京新华联生物材料有限公司 Biodegradable amylum colophony for injection molding and preparation method and products thereof
CN101942114B (en) * 2010-09-03 2012-02-08 北京新华联生物材料有限公司 Biodegradable amylum colophony for injection molding and preparation method and products thereof
CN102627935A (en) * 2012-03-23 2012-08-08 长沙乐远化工科技有限公司 Biodegradable aqueous emulsion-type polylactic acid adhesive and its preparation method
CN102627935B (en) * 2012-03-23 2013-09-25 长沙乐远化工科技有限公司 Biodegradable aqueous emulsion-type polylactic acid adhesive and its preparation method
CN103059146A (en) * 2013-02-05 2013-04-24 湘潭大学 Starch surface treatment process
CN103937036A (en) * 2014-04-23 2014-07-23 苏州羽帆新材料科技有限公司 Environment-friendly plastic containing modified starch
CN103992515A (en) * 2014-04-30 2014-08-20 安徽省宁国市明浩包装材料有限公司 High-transmittance degradable agricultural film
CN103992515B (en) * 2014-04-30 2016-11-30 刘孟香 A kind of high light transmittance degradable agricultural film
CN104151626A (en) * 2014-07-17 2014-11-19 安徽巢湖南方膜业有限责任公司 Phosphate starch-polyethylene composite plastic film and preparation method thereof
CN104151626B (en) * 2014-07-17 2016-07-06 安徽巢湖南方膜业有限责任公司 A kind of phosphate ester starch-polyethylene composite plastic film and preparation method thereof
CN104292636A (en) * 2014-09-30 2015-01-21 苏州博利迈新材料科技有限公司 Photo-and-biological double degradation composite material for lunch box and preparation method thereof
CN104441542A (en) * 2014-11-18 2015-03-25 东莞市方中运动制品有限公司 Drawing process and application of starch degradable plastics
CN104448398A (en) * 2014-11-18 2015-03-25 东莞市方中运动制品有限公司 Cassava degradable plastic as well as production process and production equipment thereof
CN104441542B (en) * 2014-11-18 2017-07-11 东莞市方中运动制品有限公司 A kind of drawing process of starch degradable plastics and its application
CN104861210A (en) * 2015-04-30 2015-08-26 亿帆鑫富药业股份有限公司 Starch-base fully biodegradable resin with steady hydrophobic property and preparation method thereof
CN106243403A (en) * 2016-08-30 2016-12-21 安徽锦鸿环保科技有限公司 A kind of tear-resistant starch degradable thin film of caprolactone grafting and preparation method thereof
CN106243404A (en) * 2016-08-30 2016-12-21 安徽锦鸿环保科技有限公司 Starch degradable thin film of caprolactone grafting that a kind of transparency is good and preparation method thereof
CN107814955A (en) * 2017-11-14 2018-03-20 成都新柯力化工科技有限公司 A kind of water resistant starch base biodegradation plastic matrix and preparation method thereof
CN107814955B (en) * 2017-11-14 2021-05-04 山西龙骏艾柯环保科技有限公司 Water-resistant starch-based biodegradable plastic master batch and preparation method thereof
CN109897327A (en) * 2019-03-06 2019-06-18 盐城市涌泉排水板有限公司 A kind of biodegradable drain bar and its preparation process
CN111019601A (en) * 2019-12-26 2020-04-17 成都新柯力化工科技有限公司 Low-cost biodegradable hot melt adhesive special for paper packaging and preparation method thereof
CN111019601B (en) * 2019-12-26 2021-06-04 绿芸加(上海)环保科技有限公司 Low-cost biodegradable hot melt adhesive special for paper packaging and preparation method thereof
CN114133629A (en) * 2021-12-25 2022-03-04 汕头市天悦科技创新研究院有限公司 Modified active starch degradation plastic master batch and preparation method thereof

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