CN101798449A - Porous media/biodegradable polymer blending material and preparation method thereof - Google Patents
Porous media/biodegradable polymer blending material and preparation method thereof Download PDFInfo
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- CN101798449A CN101798449A CN201010148728A CN201010148728A CN101798449A CN 101798449 A CN101798449 A CN 101798449A CN 201010148728 A CN201010148728 A CN 201010148728A CN 201010148728 A CN201010148728 A CN 201010148728A CN 101798449 A CN101798449 A CN 101798449A
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Abstract
The invention discloses a porous media/biodegradable polymer blending material and a preparation method thereof, relating to a biodegradable polymer material and a preparation method thereof. The invention solves the problems that a conventional thin film prepared from biodegradable polymer materials and inorganic stuffing has no water-vapor environment response property, a modified polyolefin thin film prepared from natural biodegradable materials can not be degraded completely, and a thin film prepared from natural plant fiber has complex process, high device cost and short service life. The porous media/biodegradable polymer blending material comprises biodegradable polymers with low molecular weight and high molecular weight and porous materials. The preparation method comprises the following steps of: soaking the porous materials into a biodegradable polymer solution with low molecular weight, then drying and crushing, mixing with the biodegradable polymer with high molecular weight, and extruding by using an extruder to obtain the porous media/biodegradable polymer blending material. The invention has water-vapor environment response property and environment protection, 30 to 50 MPa of tensile strength, 25 to 90 percent of breaking elongation ratio, 3 to 12 months of service life and simple process, and can be used as packaging and agricultural film materials.
Description
Technical field
The present invention relates to degradable polymer material and preparation method thereof.
Background technology
Plastics are widely used in the industry-by-industry of national economy with advantage such as its easy processing, light weight, cost is low, corrosion-resistant, easy to use.Particularly wrapping material and plastic sheeting for farm use have become the requisite that people's daily life is produced, but nondegradable plastic sheeting for farm use remains in the soil and does not decompose, can destroy the permeability of soil, reduce the water-holding capacity of soil, influence farm crop to moisture, nutrient absorbing, hinder the growth of seedlings of cereal crops root system, thereby cause the underproduction significantly of farm crop, make the arable land deterioration.What wrapping material and plastic sheeting for farm use were protected simultaneously is the object relatively more responsive to the environment water vapor condition; for example food or plant; if running off, steam causes the no longer fresh or soil drought of food than conference; if and humidity crosses conference and causes food decay or farm crop seedling rot, so have the extensive concern that the degradable film material of certain air permeability has been subjected to people.Existing degradable film material with certain air permeability has following three kinds: one, utilize degradable polymer material and mineral filler blend, being separated with filler by superpolymer in the polymeric film drawing and forming process, the principle that makes base material produce hole prepares, steam can freely pass through the hole of this film, do not have the water vapour environment response performance, can not effectively protect the moisture in the dry environment; Two, utilize starch, chitin or the cellulose modified polyolefine material of natural degradable, this film is by the degraded of natural degradable material, film degradation is fragmentated, but polyolefine wherein remains and can not degrade fully, and broken relic is easy to more fly away with buried and is difficult to cleaning, can pollute environment; Three, utilize the environmental protection film of natural plant fibre as base material, this film needs multistep technology that fiber is handled, complex process, and the equipment cost height, and also natural plant fibre is easy to degraded, and be 1 month～3 months work-ing life, and work-ing life is short.
Summary of the invention
The present invention is the problem of lacking existing complex process, equipment cost height, the work-ing life of utilizing the film of degradable polymer material and mineral filler blend preparation not have the water vapour environment response performance, utilizing the polyolefinic film of natural degradable material modification can not degrade, utilize natural plant fibre to prepare film fully in order to solve, and porous media/biodegradable polymer blending material and preparation method thereof is provided.
Porous media/biodegradable polymer blending material of the present invention is 1 by ratio of quality and the number of copies by 1 part of particle diameter
μM～50
μThe porous material of m, 0.2～2 part of low-molecular-weight biological degradation polyalcohol and 1 part～100 parts high-molecular weight biological degradation polyalcohols are formed; Wherein said low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 500Da～5000Da, and described high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 150000Da～250000Da.
Described biological degradation polyalcohol be poly(lactic acid), poly butylene succinate, polyhydroxyalkanoate, poly--
βA kind of or wherein several combination in-butyric ester, polycaprolactone, polyvinyl alcohol, carbonic acid gas/epoxy copolymerized thing, the aliphatic/aromatic copolyesters.
Described porous material is a kind of or wherein several combination in A type molecular sieve, X type molecular sieve, Y zeolite, carbonaceous molecular sieve, gac, diatomite, zeolite or the pottery.
The preparation method of porous media/biodegradable polymer blending material carries out according to the following steps: one, taking by weighing 1 part of particle diameter by ratio of quality and the number of copies is 1
μM～50
μThe porous material of m, 0.2～2 parts of low-molecular-weight biological degradation polyalcohols and 1 part～100 parts high-molecular weight biological degradation polyalcohols, wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 500Da～5000Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 150000Da～250000Da; Two, will be dissolved in the solvent through the low-molecular-weight biological degradation polyalcohol that step 1 takes by weighing, be mixed with the polymers soln that concentration is 0.17g/L～0.50g/L; Three, will join through the porous material that step 1 takes by weighing in the polymers soln of step 2 preparation and flood, dipping time is 24h～48h, then porous material is filtered out and vacuum-drying, and being ground into particle diameter then is 1
μM～50
μThe powder of m obtains being adsorbed with the porous material that hangs down the molecular biosciences degradation polymer; Four, will mix through step 4 porous material that is adsorbed with low molecular biosciences degradation polymer that obtains and the high molecular biological degradation polyalcohol that takes by weighing through step 1, extrude with twin screw extruder then, obtain porous media/biodegradable polymer blending material.
Biological degradation polyalcohol described in the step 1 be poly(lactic acid), poly butylene succinate, polyhydroxyalkanoate, poly--
βA kind of or wherein several combination in-butyric ester, polycaprolactone, polyvinyl alcohol, carbonic acid gas/epoxy copolymerized thing and the aliphatic/aromatic copolyesters;
Porous material described in the step 1 is a kind of or wherein several combination in A type molecular sieve, X type molecular sieve, Y zeolite, carbonaceous molecular sieve, gac, diatomite, zeolite and the pottery;
Solvent described in the step 2 is tetrahydrofuran (THF), trichloromethane, toluene or dimethylbenzene.
Drying described in the step 3 is performed such: if the solvent described in the step 2 is tetrahydrofuran (THF), trichloromethane or toluene, then vacuum-drying condition is: temperature be 60 ℃, vacuum tightness for-0.095MPa, time of drying be 2h～4h; If the solvent described in the step 2 is a dimethylbenzene, then vacuum-drying condition is: temperature be 100 ℃, vacuum tightness for-0.095MPa, time of drying be 2h～4h.
Porous media/biodegradable polymer blending material of the present invention is the duct of adopting lower molecular weight Biodegradable material sealing porous medium; therefore; in dry environment; this material can stop steam to pass through; the moisture of protected material can not run off; if under wet environment; lower molecular weight Biodegradable material in this material is degraded; make the duct of molecular sieve become unimpeded again; thereby make the loss of excessive moisture; so porous media/biodegradable polymer blending material of the present invention has the water vapour environment responsiveness, adopting pressure differential method (10kPa) to test its Air permenbility is 300 * 10
-6Cm
3/ m
2* d * Pa～400 * 10
-6Cm
3/ m
2* d * Pa; With the base material of high molecular biodegradable polymers as film, this material can be degraded fully, has environmental protection characteristic, in relative humidity is that complete degradation time is 240 days～300 days in 58%～62% the moistening soil, be 3 months～12 months the work-ing life of the film of the preparation of this material, long service life; Technology is that starting material are carried out mixing process, chemical reaction does not take place in process, process is simple, do not need expensive equipment yet, and be 30MPa～50MPa with the tensile strength of the film of this material preparation, elongation at break is 25%～90%, and is close with polyethylene or polypropylene general plastics machinery intensity.
Embodiment
Embodiment one: the porous media/biodegradable polymer blending material of present embodiment is 1 by ratio of quality and the number of copies by 1 part of particle diameter
μM～50
μThe porous material of m, 0.2～2 part of low-molecular-weight biological degradation polyalcohol and 1 part～100 parts high-molecular weight biological degradation polyalcohols are formed; Wherein said low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 500Da～5000Da, and described high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 150000Da～250000Da.
The porous media/biodegradable polymer blending material of present embodiment has the water vapour environment responsiveness, and adopting pressure differential method (10kPa) to test its Air permenbility is 300 * 10
-6Cm
3/ m
2* d * Pa～400 * 10
-6Cm
3/ m
2* d * Pa; With the base material of high molecular biodegradable polymers as film, this material can be degraded fully, has environmental protection characteristic, in relative humidity is that complete degradation time is 240 days～300 days in 58%～62% the moistening soil, be 3 months～12 months the work-ing life of the film of the preparation of this material, long service life; Technology is that starting material are carried out mixing process, and chemical reaction does not take place process, and process is simple, do not need expensive equipment yet, and the tensile strength of film is 30MPa～50MPa, and elongation at break is 25%～90%, has akin physical strength with polyethylene or polypropylene general plastics.
Embodiment two: what present embodiment and embodiment one were different is: described biological degradation polyalcohol be poly(lactic acid), poly butylene succinate, polyhydroxyalkanoate, poly--
βA kind of or wherein several combination in-butyric ester, polycaprolactone, polyvinyl alcohol, carbonic acid gas/epoxy copolymerized thing and the aliphatic/aromatic copolyesters.Other is identical with embodiment one.
When the biological degradation polyalcohol of present embodiment was composition, various biological degradation polyalcohols were pressed the arbitrary proportion combination.
Embodiment three: what present embodiment was different with embodiment one or two is: described porous material is a kind of or wherein several combination in A type molecular sieve, X type molecular sieve, Y zeolite, carbonaceous molecular sieve, gac, diatomite, zeolite and the pottery.Other is identical with embodiment one or two.
When the porous material of present embodiment was composition, various porous materials were pressed the arbitrary proportion combination.
Embodiment four: what present embodiment was different with one of embodiment one to three is: the porous media/biodegradable polymer blending material of present embodiment is 5 by ratio of quality and the number of copies by 1 part of particle diameter
μM～45
μThe porous material of m, 0.5～1.8 part of low-molecular-weight biological degradation polyalcohol and 10 parts～90 parts high-molecular weight biological degradation polyalcohols are formed; Wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 1000Da～3500Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 170000Da～200000Da.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different with one of embodiment one to four is: the porous media/biodegradable polymer blending material of present embodiment is 20 by ratio of quality and the number of copies by 1 part of particle diameter
μThe porous material of m, 1.5 parts of low-molecular-weight biological degradation polyalcohols and 50 parts of high-molecular weight biological degradation polyalcohols are formed; Wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 2000Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 200000Da.Other is identical with one of embodiment one to four.
Embodiment six: the preparation method of the porous media/biodegradable polymer blending material of present embodiment carries out according to the following steps: one, taking by weighing 1 part of particle diameter by ratio of quality and the number of copies is 1
μM～50
μThe porous material of m, 0.2～2 parts of low-molecular-weight biological degradation polyalcohols and 1 part～100 parts high-molecular weight biological degradation polyalcohols, wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 500Da～5000Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 150000Da～250000Da; Two, will be dissolved in the solvent through the low-molecular-weight biological degradation polyalcohol that step 1 takes by weighing, be mixed with the polymers soln that concentration is 0.17g/L～0.50g/L; Three, will join through the porous material that step 1 takes by weighing in the polymers soln of step 2 preparation and flood, dipping time is 24h～48h, then porous material is filtered out and vacuum-drying, and being ground into particle diameter then is 1
μM～50
μThe powder of m obtains being adsorbed with the porous material that hangs down the molecular biosciences degradation polymer; Four, will mix through step 4 porous material that is adsorbed with low molecular biosciences degradation polymer that obtains and the high molecular biological degradation polyalcohol that takes by weighing through step 1, extrude with twin screw extruder then, obtain porous media/biodegradable polymer blending material.
The method that twin screw extruder described in the step 4 of present embodiment is extruded is the method for prior art, and the intermingling material of preparing is granular or sheet.
The porous media/biodegradable polymer blending material of the method preparation of present embodiment has the water vapour environment responsiveness, and adopting pressure differential method (10kPa) to test its Air permenbility is 300 * 10
-6Cm
3/ m
2* d * Pa～400 * 10
-6Cm
3/ m
2* d * Pa; With the base material of high molecular biodegradable polymers as film, this material can be degraded fully, has environmental protection characteristic, and complete degradation time is 240 days～300 days in moistening soil, be 3 months～12 months the work-ing life of the film of the preparation of this material, long service life; Technological process is simple, does not also need expensive equipment, and the tensile strength of film is 30MPa～50MPa, and elongation at break is 25%～90%, has akin physical strength with polyethylene or polypropylene general plastics.
Embodiment seven: what present embodiment and embodiment six were different is: the biological degradation polyalcohol described in the step 1 be poly(lactic acid), poly butylene succinate, polyhydroxyalkanoate, poly--
βA kind of or wherein several combination in-butyric ester, polycaprolactone, polyvinyl alcohol, carbonic acid gas/epoxy copolymerized thing, the aliphatic/aromatic copolyesters.Other is identical with embodiment six.
When the biological degradation polyalcohol of present embodiment was composition, various biological degradation polyalcohols were pressed the arbitrary proportion combination.
Embodiment eight: what present embodiment was different with embodiment six or seven is: the porous material described in the step 1 is a kind of or wherein several combination in A type molecular sieve, X type molecular sieve, Y zeolite, carbonaceous molecular sieve, gac, diatomite, zeolite or the pottery.Other is identical with embodiment six or seven.
When the porous material of present embodiment was composition, various porous materials were pressed the arbitrary proportion combination.
Embodiment nine: what present embodiment was different with one of embodiment six to eight is: the solvent described in the step 2 is tetrahydrofuran (THF), trichloromethane, toluene, dimethylbenzene; Other is identical with one of embodiment six to eight.
Embodiment ten: what present embodiment was different with one of embodiment six to nine is: the drying described in the step 3 is performed such: if solvent is tetrahydrofuran (THF), trichloromethane or toluene, then vacuum-drying condition is: temperature be 60 ℃, vacuum tightness for-0.095MPa, time of drying be 2h～4h; If solvent is dimethylbenzene, then vacuum-drying condition is: temperature be 100 ℃, vacuum tightness for-0.095MPa, time of drying be 2h～4h.Other is identical with one of embodiment six to nine.
Embodiment 11: what present embodiment was different with one of embodiment six to ten is: taking by weighing 1 part of particle diameter by ratio of quality and the number of copies in the step 1 is 5
μM～45
μThe porous material of m, 0.5～1.5 parts of low-molecular-weight biological degradation polyalcohols and 10 parts～90 parts high-molecular weight biological degradation polyalcohols, wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 1000Da～3500Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 170000Da～200000Da.Other is identical with one of embodiment six to ten.
Embodiment 12: what present embodiment was different with one of embodiment six to 11 is: taking by weighing 1 part of particle diameter by ratio of quality and the number of copies in the step 1 is 30
μThe porous material of m, 1 part of low-molecular-weight biological degradation polyalcohol and 50 parts of high-molecular weight biological degradation polyalcohols, wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 2000Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 200000Da.Other is identical with one of embodiment six to 11.
Embodiment 13: what present embodiment was different with one of embodiment six to 12 is: the concentration of polymers soln is 0.2g/L～0.45g/L in the step 2.Other is identical with one of embodiment six to 12.
Embodiment 14: what present embodiment was different with one of embodiment six to 13 is: the concentration of polymers soln is 0.3g/L in the step 2.Other is identical with one of embodiment six to 13.
Embodiment 15: what present embodiment was different with one of embodiment six to 14 is: the dipping time of the porous material in the step 3 in polymers soln is 30h～40h.Other is identical with one of embodiment six to 14.
Embodiment 16: what present embodiment was different with one of embodiment six to 15 is: the dipping time of the porous material in the step 3 in polymers soln is 36h.Other is identical with one of embodiment six to 15.
Embodiment 17: what present embodiment was different with one of embodiment six to 16 is: pulverizing the back particle diameter in the step 3 is 5
μM～40
μM.Other is identical with one of embodiment six to 16.
Embodiment 18: what present embodiment was different with one of embodiment six to 17 is: pulverizing the back particle diameter in the step 3 is 20
μM.Other is identical with one of embodiment six to 17.
Embodiment 19: the preparation method of the porous media/biodegradable polymer blending material of present embodiment carries out according to the following steps: one, taking by weighing 1 part of particle diameter by ratio of quality and the number of copies is 20
μThe 5A type molecular sieve powder of m, 0.7 part of viscosity-average molecular weight are poly(lactic acid) and 12.57 parts of poly(lactic acid) that the matter average molecular weight is 210000Da of 1000; Two, the viscosity-average molecular weight that will take by weighing through step 1 is that the poly(lactic acid) of 1000Da is dissolved in the tetrahydrofuran (THF), obtains poly(lactic acid) solution, and wherein the concentration of poly(lactic acid) is 0.33g/ml; Three, will join through the 5A type molecular sieve powder that step 1 takes by weighing in the poly(lactic acid) solution of step 2 preparation and flood, dipping time is 24h, filter then and temperature be 60 ℃, vacuum tightness for the condition of-0.095MPa under vacuum-drying 3h, being crushed to particle diameter then is 20
μM obtains being adsorbed with the molecular sieve solid of poly(lactic acid); Four, the molecular sieve solid that is adsorbed with poly(lactic acid) that will obtain through step 3 and the matter average molecular weight that takes by weighing through step 1 are that the poly(lactic acid) of 210000Da mixes, and use the twin screw extruder granulation then, obtain porous media/biodegradable polymer blending material.
During twin screw extruder granulation described in the step 4, the temperature of the charging opening section of extruder barrel is 130 ℃, and the temperature of centre portion is 170 ℃, and the temperature of discharge port section is 165 ℃.
The porous media/biodegradable polymer blending material of present embodiment is the duct of adopting lower molecular weight Biodegradable material sealing porous medium; like this in dry environment; this material can stop steam to pass through; the moisture of protected material can not run off; if under wet environment; lower molecular weight Biodegradable material in this material is degraded; make the duct of molecular sieve become unimpeded again; people and make the loss of excessive moisture; so the porous media/biodegradable polymer blending material of present embodiment has the water vapour environment responsiveness; the pellet that obtains is made film with casting method; test its performance, adopting pressure differential method (10kPa) testing film Air permenbility is 312 * 10
-6Cm
3/ m
2* d * Pa; This material can be degraded fully, has environmental protection characteristic, and film complete degradation time in moistening soil is 300 days, and be 8 months～12 months the work-ing life of this film, long service life; And the tensile strength of film is 46.15MPa, and elongation at break is 27%, has akin physical strength with polyethylene or polypropylene general plastics; The preparation process technology of the porous media/biodegradable polymer blending material of present embodiment is simple, does not also need expensive equipment.
Embodiment 20: the preparation method of the porous media/biodegradable polymer blending material of present embodiment carries out according to the following steps: one, taking by weighing 1 part of particle diameter by ratio of quality and the number of copies is 20
μThe 13X molecular sieve powder of m, 0.45 part of poly butylene succinate and 3.5 parts of poly butylene succinate that the matter average molecular weight is 180000Da that viscosity-average molecular weight is 1500Da; Two, the viscosity-average molecular weight that will take by weighing through step 1 is that the poly butylene succinate of 1500Da is dissolved in the trichloromethane, obtains poly butylene succinate solution, and wherein the concentration of poly butylene succinate is 0.17g/ml; Three, will join through the 13X molecular sieve powder that step 1 takes by weighing in the poly butylene succinate solution of step 2 preparation and flood, dipping time is 36h, filter then and d to be 60 ℃, vacuum tightness in temperature be-0.095MPa vacuum-drying 2h, being ground into particle diameter then is 20
μThe powder of m obtains being adsorbed with the molecular sieve powder of poly butylene succinate; Four, the molecular sieve powder that will obtain through step 3 and the matter average molecular weight that takes by weighing through step 1 are that the poly butylene succinate of 180000Da mixes, and use the twin screw extruder granulation then, obtain porous media/biodegradable polymer blending material.
The temperature of the charging opening section of the mouth barrel of the twin screw extruder described in the present embodiment step 4 is 100 ℃, and the temperature of centre portion is 145 ℃, and the temperature of discharge port section is 140 ℃.
The porous media/biodegradable polymer blending material of present embodiment is the duct of adopting lower molecular weight Biodegradable material sealing porous medium; like this in dry environment; this material can stop steam to pass through; the moisture of protected material can not run off; if under wet environment; lower molecular weight Biodegradable material in this material is degraded; make the duct of molecular sieve become unimpeded again; people and make the loss of excessive moisture; so the porous media/biodegradable polymer blending material of present embodiment has the water vapour environment responsiveness; the pellet that obtains is made film with casting method; test its performance, adopting the Air permenbility of pressure differential method (10kPa) testing film is 355 * 10
-6Cm
3/ m
2* d * Pa; This thin-film material can be degraded fully, has environmental protection characteristic, and complete degradation time is 245 days in moistening soil, and be 7 months～9 months the work-ing life of this film, long service life; And the tensile strength of film is 31.55MPa, and elongation at break is 35%, has akin physical strength with polyethylene or polypropylene general plastics; The porous media/biodegradable polymer blending material preparation process of present embodiment is simple, does not also need expensive equipment.
Embodiment 21: the preparation method of the porous media/biodegradable polymer blending material of present embodiment carries out according to the following steps: taking by weighing 1 part of particle diameter by ratio of quality and the number of copies is 30
μThe poly butylene succinate that the diatomite of m, 0.34 part of viscosity-average molecular weight are 1800Da, 0.17 part viscosity-average molecular weight are that poly butylene succinate and 2.54 parts of matter average molecular weights that the poly(lactic acid) of 1400Da, 5.91 parts of matter average molecular weights are 180000Da are the 210000Da poly(lactic acid); Two, the viscosity-average molecular weight that will take by weighing through step 1 is that the poly butylene succinate of 1800Da and poly(lactic acid) that viscosity-average molecular weight is 1400Da are dissolved in the trichloromethane, obtains polymers soln, and wherein the concentration of poly butylene succinate is 0.12g/ml; Three, will join through the diatomite that step 1 takes by weighing in the polymers soln of step 2 preparation and flood, dipping time is 36h, filter then and temperature be 60 ℃, vacuum tightness for the condition of-0.095MPa under vacuum-drying 4h, being ground into particle diameter again is 30
μThe powder of m obtains being adsorbed with the diatomite of polymkeric substance; Four, the diatomite that will obtain through step 3 and the matter average molecular weight that takes by weighing through step 1 are that poly butylene succinate and the matter average molecular weight of 180000Da mixes for the 210000Da poly(lactic acid), use the twin screw extruder granulation then, obtain porous media/biodegradable polymer blending material.
The temperature of the charging opening section of the mouth barrel of the twin screw extruder described in the step 4 is 130 ℃, and the temperature of centre portion is 165 ℃, and the temperature of discharge port section is 155 ℃.
The porous media/biodegradable polymer blending material of present embodiment is the duct of adopting lower molecular weight Biodegradable material sealing porous medium; like this in dry environment; this material can stop steam to pass through; the moisture of protected material can not run off; if under wet environment; lower molecular weight Biodegradable material in this material is degraded; make the duct of molecular sieve become unimpeded again; people and make the loss of excessive moisture; so the porous media/biodegradable polymer blending material of present embodiment has the water vapour environment responsiveness; the pellet that obtains is made film with casting method, test its performance.Adopting the Air permenbility of pressure differential method (10kPa) testing film is 367 * 10
-6Cm
3/ m
2* d * Pa; This film material can be degraded fully, has environmental protection characteristic, and complete degradation time is 285 days in moistening soil, and be 8 months～10 months the work-ing life of film, long service life; And the tensile strength of film is 35.26MPa, and elongation at break is 89%, has akin physical strength with polyethylene or polypropylene general plastics; The technology that present embodiment prepares porous media/biodegradable polymer blending material is that starting material are carried out mixing process, and chemical reaction does not take place process, and process is simple, does not also need expensive equipment.
Claims (10)
1. porous media/biodegradable polymer blending material is characterized in that porous media/biodegradable polymer blending material is 1 by ratio of quality and the number of copies by 1 part of particle diameter
μM～50
μThe porous material of m, 0.2～2 part of low-molecular-weight biological degradation polyalcohol and 1 part～100 parts high-molecular weight biological degradation polyalcohols are formed; Wherein said low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 500Da～5000Da, and described high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 150000Da～250000Da.
2. porous media/biodegradable polymer blending material according to claim 1, it is characterized in that described biological degradation polyalcohol be poly(lactic acid), poly butylene succinate, polyhydroxyalkanoate, poly--
βA kind of or wherein several combination in-butyric ester, polycaprolactone, polyvinyl alcohol, carbonic acid gas/epoxy copolymerized thing and the aliphatic/aromatic copolyesters.
3. porous media/biodegradable polymer blending material according to claim 1 and 2 is characterized in that described porous material is a kind of or wherein several combination in A type molecular sieve, X type molecular sieve, Y zeolite, carbonaceous molecular sieve, gac, diatomite, zeolite and the pottery.
4. the preparation method of porous media/biodegradable polymer blending material as claimed in claim 1, it is characterized in that the preparation method of porous media/biodegradable polymer blending material carries out according to the following steps: one, taking by weighing 1 part of particle diameter by ratio of quality and the number of copies is 1
μM～50
μThe porous material of m, 0.2～2 part of low-molecular-weight biological degradation polyalcohol and 1 part～100 parts high-molecular weight biological degradation polyalcohols, wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 500Da～5000Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 150000Da～250000Da; Two, will be dissolved in the solvent through the low-molecular-weight biological degradation polyalcohol that step 1 takes by weighing, be mixed with the polymers soln that concentration is 0.17g/L～0.50g/L; Three, will join through the porous material that step 1 takes by weighing in the polymers soln of step 2 preparation and flood, dipping time is 24h～48h, then porous material is filtered out and vacuum-drying, and being ground into particle diameter then is 1
μM～50
μThe powder of m obtains being adsorbed with the porous material that hangs down the molecular biosciences degradation polymer; Four, will mix through step 4 porous material that is adsorbed with low molecular biosciences degradation polymer that obtains and the high molecular biological degradation polyalcohol that takes by weighing through step 1, extrude with twin screw extruder then, obtain porous media/biodegradable polymer blending material.
5. according to the preparation method of porous media/biodegradable polymer blending material according to claim 4, it is characterized in that the biological degradation polyalcohol described in the step 1 be poly(lactic acid), poly butylene succinate, polyhydroxyalkanoate, poly--
βA kind of or wherein several combination in-butyric ester, polycaprolactone, polyvinyl alcohol, carbonic acid gas/epoxy copolymerized thing and the aliphatic/aromatic copolyesters.
6. according to the preparation method of claim 4 or 5 described porous media/biodegradable polymer blending materials, it is characterized in that the porous material described in the step 1 is a kind of or wherein several combination in A type molecular sieve, X type molecular sieve, Y zeolite, carbonaceous molecular sieve, gac, diatomite, zeolite and the pottery.
7. the preparation method of porous media/biodegradable polymer blending material according to claim 6 is characterized in that the solvent described in the step 2 is tetrahydrofuran (THF), trichloromethane, toluene or dimethylbenzene.
8. according to the preparation method of claim 4,5 or 7 described porous media/biodegradable polymer blending materials, the vacuum-drying condition described in the step 3 that it is characterized in that is: if the solvent described in the step 2 is tetrahydrofuran (THF), trichloromethane or toluene, then vacuum-drying condition is: temperature be 60 ℃, vacuum tightness for-0.095MPa, time of drying be 2h～4h; If the solvent described in the step 2 is a dimethylbenzene, then vacuum-drying condition is: temperature be 100 ℃, vacuum tightness for-0.095MPa, time of drying be 2h～4h.
9. the preparation method of porous media/biodegradable polymer blending material according to claim 8 is characterized in that taking by weighing 1 part of particle diameter by ratio of quality and the number of copies in the step 1 is 5
μM～45
μThe porous material of m, 0.5～1.8 part of low-molecular-weight biological degradation polyalcohol and 10 parts～90 parts high-molecular weight biological degradation polyalcohols are formed; Wherein low-molecular-weight biological degradation polyalcohol is that viscosity-average molecular weight is the biological degradation polyalcohol of 1000Da～3500Da, and the high-molecular weight biological degradation polyalcohol is that the matter average molecular weight is the biological degradation polyalcohol of 170000Da～200000Da.
10. according to the preparation method of claim 4,5,7 or 9 described porous media/biodegradable polymer blending materials, the concentration that it is characterized in that polymers soln in the step 2 is 0.2g/L～0.45g/L.
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| CN110982259A (en) * | 2019-12-02 | 2020-04-10 | 东北林业大学 | Completely biodegradable high-barrier polyamide-based composite film material and preparation method thereof |
| CN111171537A (en) * | 2020-01-22 | 2020-05-19 | 复旦大学 | MCM-22P molecular sieve/polylactic acid composite material and preparation method thereof |
| CN111410822A (en) * | 2020-03-27 | 2020-07-14 | 四川开元创亿生物科技有限责任公司 | PBAT/P L A starch-based completely biodegradable material and preparation method thereof |
| CN116285253A (en) * | 2023-03-21 | 2023-06-23 | 贵州省材料产业技术研究院 | Thermal-insulation biodegradable water-permeable mulching film and preparation method thereof |
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2010
- 2010-04-16 CN CN2010101487280A patent/CN101798449B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982259A (en) * | 2019-12-02 | 2020-04-10 | 东北林业大学 | Completely biodegradable high-barrier polyamide-based composite film material and preparation method thereof |
| CN111171537A (en) * | 2020-01-22 | 2020-05-19 | 复旦大学 | MCM-22P molecular sieve/polylactic acid composite material and preparation method thereof |
| CN111410822A (en) * | 2020-03-27 | 2020-07-14 | 四川开元创亿生物科技有限责任公司 | PBAT/P L A starch-based completely biodegradable material and preparation method thereof |
| CN116285253A (en) * | 2023-03-21 | 2023-06-23 | 贵州省材料产业技术研究院 | Thermal-insulation biodegradable water-permeable mulching film and preparation method thereof |
| CN116285253B (en) * | 2023-03-21 | 2024-04-26 | 贵州省材料产业技术研究院 | Thermal-insulation biodegradable water-permeable mulching film and preparation method thereof |
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