CN103951919B - Polyvinyl alcohol composite master batch and preparation method thereof - Google Patents
Polyvinyl alcohol composite master batch and preparation method thereof Download PDFInfo
- Publication number
- CN103951919B CN103951919B CN201410140344.2A CN201410140344A CN103951919B CN 103951919 B CN103951919 B CN 103951919B CN 201410140344 A CN201410140344 A CN 201410140344A CN 103951919 B CN103951919 B CN 103951919B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- poly
- polyhydroxyalkanoate
- master batch
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a polyvinyl alcohol composite master batch and a preparation method thereof. The polyvinyl alcohol composite master batch is a blend comprising polyvinyl alcohol, and polyhydroxyalkanoate; the weight content of the polyvinyl alcohol is 51-99%, and the weight content of the polyhydroxyalkanoate is 1-49%. The method comprises the following steps: well mixing polyvinyl alcohol powder with polyhydroxyalkanoate powder, adding deionized water, and well mixing to obtain a mixture; drying the mixture, injecting the mixture into a screw extruder with a heating device, melting at 175-185 DEG C for 4-8 min, performing melt extrusion and natural cooling to normal temperature, and cutting into particles by a pelletizer. The material is a novel environment friendly material, can degrade naturally after being used and discarded, and causes no environment burden; the material has significantly decreased melt viscosity at a relatively low temperature range and a wide shearing rate range, and has excellent thermoplastic processing performance.
Description
Technical field
The invention belongs to polymeric material field is and in particular to a kind of polyvinyl alcohol composite master batch and preparation method thereof.
Background technology
Polyvinyl alcohol (pva) is a kind of water-soluble biological degradable macromolecule, has excellent machinery, physics, chemical
Energy and film property, are widely used in the fields such as thin film, fiber, binding agent, paper making additive.But, contain substantial amounts of in pva main chain
Hydroxyl, intermolecular and intramolecular forms a large amount of hydrogen bonds so that its fusing point is close with decomposition temperature, and the thermoplastic being difficult to carry out routine adds
Work.And the solution wet moulding of routine, such as solution cast film formation etc., need to experience dissolving and the dry run of resin, there is work
The shortcomings of skill complexity, high cost, low yield, wastewater discharge are big.Although China is the production and consumption big country of pva product,
The production technology of pva still, based on traditional solution machine-shaping, is unfavorable for industry development.Therefore, realize the thermoplastic processing of pva
Significant.
At present, the known method realizing pva thermoplastic processing is to add the small-molecule substances such as water, alcohols, caprolactam, leads to
Cross fusing point and the shear viscosity that plasticization reduces pva.As document [polymer science and engineering, 2008,24(5): 84-87] will
Glycerol, Polyethylene Glycol, caprolactam etc. make Compositional type Plasticising system, soluble in water with pva make pva- Plasticising system, permissible
Effectively reduce melt index, reduce the fusing point of pva, improve heat decomposition temperature, improve product appearance.Publication No.
The Chinese invention patent of 10313698a proposes a kind of plasticizer formula of confession pva thermoplastic processing and processing technique, realizes
The thermoplastic processing of pva.But, volatile, the precipitation from product at higher processing temperatures of organic molecule plasticizer itself,
Thus affecting the serviceability of product.Alcaminess modifying agent as document [Chinese Plastics, 2003,17(2): 60-62] is reported increases
Mould in pva system, pva plasticizing capacity is deteriorated with the increase of pva alcoholysis degree.And document [plastics industry, 2002,30(1):
32-34] research of pva plasticising is shown: there is long-term placement and easily analyse in the amide organic micromolecule for pva is carried out with plasticising
The problem going out.The Chinese patent of Publication No. cn102391598a reports a kind of production method of polyvinyl alcohol material, its skill
Art feature be by plasticizer under conditions of with the presence of water plasticising pva, carry out hot melt under less than polyvinyl alcohol decomposition temperature and add
Work, but water is readily volatilized at relatively high temperatures, and usually work in-process produces bubble and produces it is impossible to realize stable and continuous.
Obviously, the thermoplastic processing of pva is technological difficulties and the research and development focus of this technical field.Currently known technology is all logical
Cross the small-molecule substance such as interpolation water, glycerol in pva and plasticising is carried out to it, thus bring plasticizer residual, separate out, and in heat
Mould and in the course of processing, produce the problems such as bubble, flaw.It would therefore be highly desirable to develop new technology to realize the thermoplastic processing of pva, and
Avoid the various problems brought by small molecule plasticising.
Content of the invention
It is an object of the invention to being directed to the deficiencies in the prior art, provide a kind of polyvinyl alcohol composite master batch.
The polyvinyl alcohol composite master batch of the present invention is blend, and this blend includes polyvinyl alcohol, polyhydroxyalkanoate；
The weight content of wherein polyvinyl alcohol is 51～99, and the weight content of polyhydroxyalkanoate is 1～49,175～185
℃、100s-1Under conditions of shear rate, the apparent shear viscosity of polyvinyl alcohol composite master batch is less than 20000pa s, has good
Thermoplastic processability；
Preferably, the weight content of polyvinyl alcohol is 60～90 in polyvinyl alcohol composite master batch, poly-hydroxy fatty acid
The weight content of ester is 10～40, in 175～185 DEG C, 100s-1The table of polyvinyl alcohol composite master batch under conditions of shear rate
See shear viscosity and be less than 10000pa s, there is good thermoplastic processability.
It is a further object to provide the preparation method of above-mentioned polyvinyl alcohol composite master batch.
The inventive method comprises the following steps:
Step (1). pva powder and polyhydroxyalkanoate powder are carried out first time physical mixed uniformly, then
Add deionized water to carry out second physical mixed, after mix homogeneously, obtain compound；Wherein pva powder and poly- hydroxyl
For 51:49～99:1, the weight of deionized water is pva powder and poly-hydroxy fatty acid to the weight of fatty acid ester powder ratio
The 0.5～1.5 of ester powder gross weight；
Preferably, the weight of pva powder and polyhydroxyalkanoate powder is than for 6:4～9:1；
The equal particle diameter of number of described pva powder is 0.01～0.1mm, and average degree of polymerization is 600～1800,
Alcoholysis degree is 88～99.8 (mol/mol)；
Preferably, the equal particle diameter of the number of pva powder be 0.01～0.055mm, average degree of polymerization be 600～
1000, alcoholysis degree is 88～99.8 (mol/mol)；
The equal particle diameter of number of described polyhydroxyalkanoate powder is 0.01～0.1mm, has following chemical constitution
Formula:
In formula: r1、r2Each stand alone as h, methyl ch3Or ethyl c2h5；M1, m2 each stand alone as 1 or 2；X, y are each independent
For 0 or 200～20000 random natural number, and it is 0 when x, y are different.
Preferably, r in the described chemical structure of general formula of polyhydroxyalkanoate powder1For methyl ch3, m1 be 1, x be
200～20000 random natural number, y be 0 when be poly 3-hydroxy butyrate (p-3hb), its number equal particle diameters be 0.01～
0.1mm, volume crystallinity is 30～70, weight average molecular weight is 9～650,000；
Preferably, described polyhydroxyalkanoate powder r in formula1For h, m1 be 2, x be 200～20000
Random natural number, y are to be poly- 4 hydroxybutyric acid ester (p-4hb) when 0, and its equal particle diameter of number is 0.01～0.1mm, volume crystallization
Spending for 30～70, weight average molecular weight is 9～650,000；
Preferably, described polyhydroxyalkanoate powder r in formula1For ethyl c2h5, m1 be 1, x be 200～
20000 random natural number, y are to be poly- 3- hydroxyl valerate (p-3hv) when 0, and its equal particle diameter of number is 0.01～0.1mm,
Volume crystallinity is 15～55, weight average molecular weight is 9～650,000；
Preferably, described polyhydroxyalkanoate powder r in formula1For methyl ch3、r2It is that 1, m2 is for h, m1
2nd, x and y is during 200～20000 random natural number is poly- 3-hydroxybutyrate -4 hydroxybutyric acid copolyesters (p-3hb-4hb),
Its equal particle diameter of number is 0.01～0.1mm, and volume crystallinity is 10～50, weight average molecular weight is 9～750,000,4- therein
The molar content of butyric ester (p-4hb) is 1～45；
Preferably, described polyhydroxyalkanoate powder r in formula1For methyl ch3、r2For ethyl c2h5, m1 and
M2 be 1, x and y be 200～20000 random natural number when be poly butyric-valeric acid copolyesters (phbv), its number is all
Particle diameter is 0.01～0.1mm, and volume crystallinity is 15～65, weight average molecular weight is 9～750,000,3- hydroxyl penta therein
The molar content of acid esters (p-3hv) is 1～45；
Step (2). it is constant that the compound obtaining step (1) is dried under vacuum to constant weight in 60～100 DEG C, and it is unnecessary to remove
Moisture；
Step (3). the injection of dried for step (2) compound is carried in the screw extruder of heater, screw rod
Draw ratio melts 4～8 minutes at being 10～30,175～185 DEG C, melt extrudes and obtains melt extrusion；
Step (4). step (3) melt extrusion is naturally cooled to room temperature, pelletizer in atmosphere, preparing can
Particulate polyethylene alcohol composite master batch for thermoplastic processing.
The polyvinyl alcohol composite master batch of the present invention comprises to be biodegradable polyvinyl alcohol and polyhydroxyalkanoate
Component, is a kind of novel environmental friendly materials, using energy natural degradation after discarding, environment is not caused to bear.This polyethylene
Alcohol composite master batch has significantly reduced melt viscosity in relatively low temperature range and wider range of shear rate, tool
There is excellent thermoplastic processing characteristic.The present invention passes through many experiments, finds only to work as polyvinyl alcohol and polyhydroxyalkanoate
Structural parameters (particle diameter, average degree of polymerization, alcoholysis degree, chemical constitution, molecular weight, degree of crystallinity, co-monomer content) meet specific
During condition, the two could occur the hydroxyl of appropriateness to interact, and makes the original hydrogen bond of polyvinyl alcohol weakened, simultaneously poly- hydroxyl fat
Fat acid esters dispersion phase deforms, is orientated, thus reducing the melt viscosity of compound system.This polyvinyl alcohol composite master batch avoids
Conventional method adds the small-molecule substances such as water, glycerol for realizing polyvinyl alcohol thermoplastic processing, solves small-molecule substance and is adding
During work produce bubble, use during separate out the problems such as, contribute to improving the outward appearance homogeneity of product and stability.
The present invention also proposes the preparation method of above-mentioned polyvinyl alcohol composite master batch, by first time physical mixed make pva powder with
Polyhydroxyalkanoate powder is dispersed；Pass through second physical mixed again and add appropriate water, make pva powder table
There is shallow-layer dissolving in face, increase the cohesive between pva powder and polyhydroxyalkanoate powder；Then control melting
The temperature and time window of extrusion, is prevented effectively from the thermal degradation of polyvinyl alcohol while guaranteeing that compound system is dispersed.
Specific embodiment
With reference to embodiment, technical scheme and effect are further described.Polyvinyl alcohol in embodiment
The apparent shear viscosity of composite master batch adopts model gottferttm, the capillary rheometer determining of rheo-tester2000.
Pva powder in embodiment is within the temperature range of 175～185 DEG C and 100s-1Shear rate under apparent shearing stick
Degree is above 20000pa s it is impossible to smoothly melt extrude.
Embodiment 1:
Equal particle diameter of peeking is 0.01mm, average degree of polymerization is the polyethylene that 600, alcoholysis degree is 88 (mol/mol)
The poly- 3- hydroxyl that 90 kilograms of alcohol powder and the equal particle diameters of number are 0.01mm, volume crystallinity is 70, weight average molecular weight is 90,000
10 kilograms of butyrate (p-3hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, and the time is
3～5 minutes；It is subsequently adding 1.5 kilograms of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 minutes；
Compound is vacuum dried 6 hours at 100 DEG C, removes excessive moisture；Dried compound injection screw slenderness ratio is
In 30 single screw extrusion machine, melt extrude at 175 DEG C, it is 8 minutes that adjustment screw speed makes the melting time of compound；Will
Melt extrusion natural cooling in atmosphere, pelletizer, prepare milky, the particulate polyethylene alcohol of smooth surface is answered
Combination master batch.Through capillary rheometer determining, this masterbatch temperature be 175 DEG C, shear rate be 100,1000,10000s-1Under
Apparent shear viscosity be respectively 9520,3730,510pa s, there is good thermoplastic processability.
Embodiment 2:
Equal particle diameter of peeking is 0.0325mm, average degree of polymerization is that 800, alcoholysis degree is poly- for 93.9 (mol/mol)
75 kilograms of vinyl alcohol powder and the equal particle diameters of number are 0.0325mm, volume crystallinity is 50, weight average molecular weight is 370,000
25 kilograms of poly 3-hydroxy butyrate (p-3hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is normal
Temperature, the time is 3～5 minutes；Be subsequently adding 1 kilogram of water, carry out second physical mixed, mixing temperature be room temperature, the time be 3～
5 minutes；Compound is vacuum dried 6 hours at 80 DEG C, removes excessive moisture；Dried compound is injected screw rod major diameter
Ratio, in the single screw extrusion machine for 20, melt extrudes at 180 DEG C, and adjustment screw speed makes the melting time of compound be 4 points
Clock；By melt extrusion natural cooling in atmosphere, pelletizer, prepare the poly- second of graininess of milky, smooth surface
Enol composite master batch.Through capillary rheometer determining, this masterbatch temperature be 180 DEG C, shear rate be 100,1000,
10000s-1Under apparent shear viscosity be respectively 9600,3980,530pa s, there is good thermoplastic processability.
Embodiment 3:
Equal particle diameter of peeking is 0.055mm, average degree of polymerization is that 1000, alcoholysis degree is poly- for 99.8 (mol/mol)
60 kilograms of vinyl alcohol powder and the equal particle diameters of number are 0.055mm, volume crystallinity is 30, weight average molecular weight be 650,000 poly-
40 kilograms of 3-hydroxybutyrate ester (p-3hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature,
Time is 3～5 minutes；It is subsequently adding 0.5 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5
Minute；Compound is vacuum dried 8 hours at 60 DEG C, removes excessive moisture；Dried compound is injected screw rod major diameter
Ratio, in the conical double screw extruder for 10, melt extrudes at 185 DEG C, and adjustment screw speed makes the melting time of compound be
6 minutes；By melt extrusion natural cooling in atmosphere, pelletizer, prepare milky, the graininess of smooth surface is gathered
Vinyl alcohol composite master batch.Through capillary rheometer determining, this masterbatch temperature be 185 DEG C, shear rate be 100,1000,
10000s-1Under apparent shear viscosity be respectively 9850,4160,550pa s, there is good thermoplastic processability.
Embodiment 4:
Equal particle diameter of peeking is 0.0325mm, average degree of polymerization is that 600, alcoholysis degree is poly- for 93.9 (mol/mol)
60 kilograms of vinyl alcohol powder and the equal particle diameters of number are 0.055mm, volume crystallinity is 70, weight average molecular weight be 370,000 poly-
40 kilograms of 4 hydroxybutyric acid ester (p-4hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature,
Time is 3～5 minutes；It is subsequently adding 0.5 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5
Minute；Compound is vacuum dried 6 hours at 80 DEG C, removes excessive moisture；Dried compound is injected screw rod major diameter
Ratio, in the single screw extrusion machine for 30, melt extrudes at 175 DEG C, and adjustment screw speed makes the melting time of compound be 6 points
Clock；By melt extrusion natural cooling in atmosphere, pelletizer, prepare the poly- second of graininess of milky, smooth surface
Enol composite master batch.Through capillary rheometer determining, this masterbatch temperature be 175 DEG C, shear rate be 100,1000,
10000s-1Under apparent shear viscosity be respectively 8400,2550,405pa s, there is good thermoplastic processability.
Embodiment 5:
Equal particle diameter of peeking is 0.01mm, average degree of polymerization is the poly- second that 800, alcoholysis degree is 99.8 (mol/mol)
The poly- 4- hydroxyl that 90 kilograms of enol powder and the equal particle diameters of number are 0.01mm, volume crystallinity is 50, weight average molecular weight is 90,000
10 kilograms of base butyrate (p-4hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, the time
For 3～5 minutes；It is subsequently adding 1.5 kilograms of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 6 hours at 100 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 10 conical double screw extruder, melt extruding at 185 DEG C, it is 8 that adjustment screw speed makes the melting time of compound
Minute；By melt extrusion natural cooling in atmosphere, pelletizer, prepare milky, the graininess of smooth surface is gathered
Vinyl alcohol composite master batch.Through capillary rheometer determining, this masterbatch temperature be 185 DEG C, shear rate be 100,1000,
10000s-1Under apparent shear viscosity be respectively 9650,4110,560pa s, there is good thermoplastic processability.
Embodiment 6:
Equal particle diameter of peeking is 0.055mm, average degree of polymerization is the poly- second that 1000, alcoholysis degree is 88 (mol/mol)
75 kilograms of enol powder and the equal particle diameters of number are 0.0325mm, volume crystallinity is 30, weight average molecular weight be 650,000 poly-
25 kilograms of 4 hydroxybutyric acid ester (p-4hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature,
Time is 3～5 minutes；It is subsequently adding 1 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 10 hours at 60 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 20 single screw extrusion machine, melt extruding at 180 DEG C, it is 4 minutes that adjustment screw speed makes the melting time of compound；
By melt extrusion natural cooling in atmosphere, pelletizer, prepare the particulate polyethylene alcohol of milky, smooth surface
Composite master batch.Through capillary rheometer determining, this masterbatch temperature be 180 DEG C, shear rate be 100,1000,10000s-1Under
Apparent shear viscosity be respectively 9800,4230,575pa s, there is good thermoplastic processability.
Embodiment 7:
Equal particle diameter of peeking is 0.055mm, average degree of polymerization is the poly- second that 600, alcoholysis degree is 99.8 (mol/mol)
The poly- 3- that 60 kilograms of enol powder and the equal particle diameters of number are 0.055mm, volume crystallinity is 15, weight average molecular weight is 90,000
40 kilograms of hydroxyl valerate (p-3hv) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, when
Between be 3～5 minutes；It is subsequently adding 0.5 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 8 hours at 60 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 30 single screw extrusion machine, melt extruding at 175 DEG C, it is 4 minutes that adjustment screw speed makes the melting time of compound；
By melt extrusion natural cooling in atmosphere, pelletizer, prepare the particulate polyethylene alcohol of milky, smooth surface
Composite master batch.Through capillary rheometer determining, this masterbatch temperature be 175 DEG C, shear rate be 100,1000,10000s-1Under
Apparent shear viscosity be respectively 7420,2300,382pa s, there is good thermoplastic processability
Embodiment 8:
Equal particle diameter of peeking is 0.0325mm, average degree of polymerization is the poly- second that 800, alcoholysis degree is 88 (mol/mol)
75 kilograms of enol powder and the equal particle diameters of number are 0.0325mm, volume crystallinity is 35, weight average molecular weight be 650,000 poly-
25 kilograms of 3- hydroxyl valerate (p-3hv) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature,
Time is 3～5 minutes；It is subsequently adding 1 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 6 hours at 80 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 20 single screw extrusion machine, melt extruding at 180 DEG C, it is 6 minutes that adjustment screw speed makes the melting time of compound；
By melt extrusion natural cooling in atmosphere, pelletizer, prepare the particulate polyethylene alcohol of milky, smooth surface
Composite master batch.Through capillary rheometer determining, this masterbatch temperature be 180 DEG C, shear rate be 100,1000,10000s-1Under
Apparent shear viscosity be respectively 9510,3860,525pa s, there is good thermoplastic processability.
Embodiment 9:
Equal particle diameter of peeking is 0.01mm, average degree of polymerization is the poly- second that 1000, alcoholysis degree is 93.9 (mol/mol)
The poly- 3- that 90 kilograms of enol powder and the equal particle diameters of number are 0.01mm, volume crystallinity is 55, weight average molecular weight is 370,000
10 kilograms of hydroxyl valerate (p-3hv) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, when
Between be 3～5 minutes；It is subsequently adding 1.5 kilograms of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 6 hours at 100 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 10 double screw extruder, melt extruding at 185 DEG C, it is 8 minutes that adjustment screw speed makes the melting time of compound；
By melt extrusion natural cooling in atmosphere, pelletizer, prepare the particulate polyethylene alcohol of milky, smooth surface
Composite master batch.Through capillary rheometer determining, this masterbatch temperature be 185 DEG C, shear rate be 100,1000,10000s-1Under
Apparent shear viscosity be respectively 9850,4260,580pa s, there is good thermoplastic processability.
Embodiment 10:
Equal particle diameter of peeking is 0.055mm, average degree of polymerization is the poly- second that 600, alcoholysis degree is 99.8 (mol/mol)
90 kilograms of enol powder and the equal particle diameter of number are 0.01mm, volume crystallinity be 30, weight average molecular weight is 750,000,4- hydroxyl
Butyrate (p-4hb) molar content is 23 poly- 3-hydroxybutyrate -4 hydroxybutyric acid copolyesters (p-3hb-4hb) powder 10,000
Gram carry out first time physical mixed in homogenizer, mixing temperature is room temperature, the time is 3～5 minutes；It is subsequently adding 1.5
Kilogram water, carries out second physical mixed, and mixing temperature is room temperature, and the time is 3～5 minutes；By compound at 60 DEG C vacuum
It is dried 10 hours, remove excessive moisture；Dried compound injection screw slenderness ratio is in 10 single screw extrusion machine,
Melt extrude at 185 DEG C, it is 4 minutes that adjustment screw speed makes the melting time of compound；Melt extrusion is natural in atmosphere
Cooling, pelletizer, prepare the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheology
Instrument measure, this masterbatch temperature be 185 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively
7250th, 2260,370pa s, has good thermoplastic processability.Embodiment 11:
Equal particle diameter of peeking is 0.01mm, average degree of polymerization is the poly- second that 800, alcoholysis degree is 93.9 (mol/mol)
60 kilograms of enol powder and the equal particle diameter of number are 0.055mm, volume crystallinity be 50, weight average molecular weight is 90,000,4- hydroxyl
Butyrate (p-4hb) molar content is 1 poly- 3-hydroxybutyrate -4 hydroxybutyric acid copolyesters (p-3hb-4hb) powder 40,000
Gram carry out first time physical mixed in homogenizer, mixing temperature is room temperature, the time is 3～5 minutes；It is subsequently adding 0.5
Kilogram water, carries out second physical mixed, and mixing temperature is room temperature, and the time is 3～5 minutes；By compound at 80 DEG C vacuum
It is dried 5 hours, remove excessive moisture；The conical double screw extruder that dried compound injection screw slenderness ratio is 20
In, melt extrude at 175 DEG C, it is 8 minutes that adjustment screw speed makes the melting time of compound；By melt extrusion in atmosphere
Natural cooling, pelletizer, prepare the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary tube
Rheometer measurement, this masterbatch temperature be 175 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity respectively
For 7080,2100,353pa s, there is good thermoplastic processability.Embodiment 12:
Equal particle diameter of peeking is 0.0325mm, average degree of polymerization is the poly- second that 1000, alcoholysis degree is 88 (mol/mol)
75 kilograms of enol powder and the equal particle diameter of number are 0.0325mm, volume crystallinity be 10, weight average molecular weight is 420,000,4- hydroxyl
Base butyrate (p-4hb) molar content is 45 poly- 3-hydroxybutyrate -4 hydroxybutyric acid copolyesters (p-3hb-4hb) powder 25
Kilogram carry out first time physical mixed in homogenizer, mixing temperature is room temperature, the time is 3～5 minutes；It is subsequently adding 1
Kilogram water, carries out second physical mixed, and mixing temperature is room temperature, and the time is 3～5 minutes；By compound at 60 DEG C vacuum
It is dried 8 hours, remove excessive moisture；Dried compound injection screw slenderness ratio is in 30 single screw extrusion machine,
Melt extrude at 180 DEG C, it is 6 minutes that adjustment screw speed makes the melting time of compound；Melt extrusion is natural in atmosphere
Cooling, pelletizer, prepare the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheology
Instrument measure, this masterbatch temperature be 180 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively
7200th, 2210,360pa s, has good thermoplastic processability.Embodiment 13:
Equal particle diameter of peeking is 0.01mm, average degree of polymerization is the poly- second that 600, alcoholysis degree is 99.8 (mol/mol)
75 kilograms of enol powder and the equal particle diameter of number are 0.0325mm, volume crystallinity be 40, weight average molecular weight is 90,000,3- hydroxyl
Base valerate (p-3hv) molar content be 23 poly butyric -25 kilograms of valeric acid copolyesters (phbv) powder in high-speed stirring
Mix and in machine, carry out first time physical mixed, mixing temperature is room temperature, the time is 3～5 minutes；It is subsequently adding 1 kilogram of water, carry out
Secondary physical mixes, and mixing temperature is room temperature, and the time is 3～5 minutes；Compound is vacuum dried 8 hours at 60 DEG C, removes
Excessive moisture；Dried compound injection screw slenderness ratio is in 10 conical double screw extruder, melts at 175 DEG C
Extrusion, it is 6 minutes that adjustment screw speed makes the melting time of compound；By melt extrusion natural cooling in atmosphere, comminutor
Pelletizing, prepares the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheometer determining, this mother
Material temperature be 175 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively 7430,2290,
378pa s, has good thermoplastic processability.
Embodiment 14:
Equal particle diameter of peeking is 0.0325mm, average degree of polymerization is the poly- second that 800, alcoholysis degree is 88 (mol/mol)
90 kilograms of enol powder and the equal particle diameter of number are 0.01mm, volume crystallinity be 15, weight average molecular weight is 420,000,3- hydroxyl
Valerate (p-3hv) molar content be 45 poly butyric -10 kilograms of valeric acid copolyesters (phbv) powder in high-speed stirred
Carry out first time physical mixed, mixing temperature is room temperature, the time is 3～5 minutes in machine；It is subsequently adding 1.5 kilograms of water, carry out
Secondary physical mixes, and mixing temperature is room temperature, and the time is 3～5 minutes；Compound is vacuum dried 6 hours at 100 DEG C, removes
Remove excessive moisture；Dried compound injection screw slenderness ratio is in 20 single screw extrusion machine, melts at 185 DEG C and squeeze
Go out, it is 4 minutes that adjustment screw speed makes the melting time of compound；By melt extrusion natural cooling in atmosphere, comminutor is cut
Grain, prepares the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheometer determining, this masterbatch
Temperature be 185 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively 7500,2320,
390pa s, has good thermoplastic processability.
Embodiment 15:
Equal particle diameter of peeking is 0.055mm, average degree of polymerization is that 1000, alcoholysis degree is poly- for 93.9 (mol/mol)
60 kilograms of vinyl alcohol powder and the equal particle diameter of number are 0.055mm, volume crystallinity be 65, weight average molecular weight is 750,000,3-
Hydroxyl valerate (p-3hv) molar content be 1 poly butyric -40 kilograms of valeric acid copolyesters (phbv) powder in high-speed stirring
Mix and in machine, carry out first time physical mixed, mixing temperature is room temperature, the time is 3～5 minutes；It is subsequently adding 0.5 kilogram of water, carry out
Second physical mixed, mixing temperature is room temperature, and the time is 3～5 minutes；Compound is vacuum dried 6 hours at 80 DEG C, removes
Remove excessive moisture；Dried compound injection screw slenderness ratio is in 20 single screw extrusion machine, melts at 180 DEG C and squeeze
Go out, it is 8 minutes that adjustment screw speed makes the melting time of compound；By melt extrusion natural cooling in atmosphere, comminutor is cut
Grain, prepares the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheometer determining, this masterbatch
Temperature be 180 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively 7540,2400,
400pa s, has good thermoplastic processability.
Embodiment 16:
Equal particle diameter of peeking is 0.01mm, average degree of polymerization is the polyethylene that 1200, alcoholysis degree is 88 (mol/mol)
The poly- 3- hydroxyl that 75 kilograms of alcohol powder and the equal particle diameters of number are 0.055mm, volume crystallinity is 55, weight average molecular weight is 370,000
25 kilograms of base valerate (p-3hv) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, the time
For 3～5 minutes；It is subsequently adding 1 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 minutes；
Compound is vacuum dried 6 hours at 80 DEG C, removes excessive moisture；Dried compound injection screw slenderness ratio is 30
Single screw extrusion machine in, melt extrude at 180 DEG C, adjustment screw speed make compound melting time be 6 minutes；To squeeze
Go out melt natural cooling in atmosphere, pelletizer, prepare milky, the particulate polyethylene alcohol of smooth surface is combined
Masterbatch.Through capillary rheometer determining, this masterbatch temperature be 180 DEG C, shear rate be 100,1000,10000s-1Under table
See shear viscosity be respectively 9600,4100,550pa s, there is good thermoplastic processability.
Embodiment 17:
Equal particle diameter of peeking is 0.1mm, average degree of polymerization is the poly- second that 1800, alcoholysis degree is 93.9 (mol/mol)
The poly- 4- hydroxyl that 51 kilograms of enol powder and the equal particle diameters of number are 0.1mm, volume crystallinity is 70, weight average molecular weight is 650,000
49 kilograms of base butyrate (p-4hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, the time
For 3～5 minutes；It is subsequently adding 0.5 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 6 hours at 100 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 10 single screw extrusion machine, melt extruding at 185 DEG C, it is 4 minutes that adjustment screw speed makes the melting time of compound；
By melt extrusion natural cooling in atmosphere, pelletizer, prepare the particulate polyethylene alcohol of milky, smooth surface
Composite master batch.Through capillary rheometer determining, this masterbatch temperature be 185 DEG C, shear rate be 100,1000,10000s-1Under
Apparent shear viscosity be respectively 8850,2920,448pa s, there is good thermoplastic processability.
Embodiment 18:
Equal particle diameter of peeking is 0.055mm, average degree of polymerization is the poly- second that 600, alcoholysis degree is 99.8 (mol/mol)
99 kilograms of enol powder and the equal particle diameter of number are 0.01mm, volume crystallinity be 65, weight average molecular weight is 90,000,3- hydroxyl
Valerate (p-3hv) molar content be 1 poly butyric -1 kilogram of valeric acid copolyesters (phbv) powder in homogenizer
In carry out first time physical mixed, mixing temperature be room temperature, the time be 3～5 minutes；It is subsequently adding 1.5 kilograms of water, carry out second
Secondary physical mixed, mixing temperature is room temperature, and the time is 3～5 minutes；Compound is vacuum dried 10 hours at 60 DEG C, removes
Excessive moisture；Dried compound injection screw slenderness ratio is in 20 double screw extruder, melts at 175 DEG C and squeeze
Go out, it is 8 minutes that adjustment screw speed makes the melting time of compound；By melt extrusion natural cooling in atmosphere, comminutor is cut
Grain, prepares the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheometer determining, this masterbatch
Temperature be 175 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively 10030,3110,
452pa s, has good thermoplastic processability.
Embodiment 19:
Equal particle diameter of peeking is 0.055mm, average degree of polymerization is the poly- second that 1000, alcoholysis degree is 88 (mol/mol)
The poly- 3- hydroxyl that 60 kilograms of enol powder and the equal particle diameters of number are 0.1mm, volume crystallinity is 55, weight average molecular weight is 370,000
40 kilograms of base valerate (p-3hv) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, the time
For 3～5 minutes；It is subsequently adding 0.5 kilogram of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 6 hours at 80 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 30 single screw extrusion machine, melt extruding at 175 DEG C, it is 4 minutes that adjustment screw speed makes the melting time of compound；
By melt extrusion natural cooling in atmosphere, pelletizer, prepare the particulate polyethylene alcohol of milky, smooth surface
Composite master batch.Through capillary rheometer determining, this masterbatch temperature be 175 DEG C, shear rate be 100,1000,10000s-1Under
Apparent shear viscosity be respectively 8600,2730,425pa s, there is good thermoplastic processability.
Embodiment 20:
Equal particle diameter of peeking is 0.0325mm, average degree of polymerization is the poly- second that 800, alcoholysis degree is 88 (mol/mol)
90 kilograms of enol powder and the equal particle diameter of number are 0.1mm, volume crystallinity be 40, weight average molecular weight is 500,000,3- hydroxyl
Valerate (p-3hv) molar content be 45 poly butyric -10 kilograms of valeric acid copolyesters (phbv) powder in high-speed stirred
Carry out first time physical mixed, mixing temperature is room temperature, the time is 3～5 minutes in machine；It is subsequently adding 1.5 kilograms of water, carry out
Secondary physical mixes, and mixing temperature is room temperature, and the time is 3～5 minutes；Compound is vacuum dried 6 hours at 100 DEG C, removes
Remove excessive moisture；Dried compound injection screw slenderness ratio is in 20 single screw extrusion machine, melts at 185 DEG C and squeeze
Go out, it is 4 minutes that adjustment screw speed makes the melting time of compound；By melt extrusion natural cooling in atmosphere, comminutor is cut
Grain, prepares the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheometer determining, this masterbatch
Temperature be 185 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively 9000,3020,
460pa s, has good thermoplastic processability.
Embodiment 21:
Equal particle diameter of peeking is 0.0325mm, average degree of polymerization is the poly- second that 1000, alcoholysis degree is 88 (mol/mol)
75 kilograms of enol powder and the equal particle diameter of number are 0.1mm, volume crystallinity be 10, weight average molecular weight is 420,000,4- hydroxyl
Butyrate (p-4hb) molar content is 45 poly- 3-hydroxybutyrate -4 hydroxybutyric acid copolyesters (p-3hb-4hb) powder 25,000
Gram carry out first time physical mixed in homogenizer, mixing temperature is room temperature, the time is 3～5 minutes；It is subsequently adding 1,000
Gram water, carries out second physical mixed, and mixing temperature is room temperature, and the time is 3～5 minutes；By compound, at 60 DEG C, vacuum is done
Dry 8 hours, remove excessive moisture；Dried compound injection screw slenderness ratio is in 30 single screw extrusion machine, 180
Melt extrude at DEG C, it is 6 minutes that adjustment screw speed makes the melting time of compound；Melt extrusion is naturally cold in atmosphere
But, pelletizer, prepares the particulate polyethylene alcohol composite master batch of milky, smooth surface.Through capillary rheometer
Measure, this masterbatch temperature be 180 DEG C, shear rate be 100,1000,10000s-1Under apparent shear viscosity be respectively
6750th, 1900,310pa s, has good thermoplastic processability.
Embodiment 22:
Equal particle diameter of peeking is 0.01mm, average degree of polymerization is the poly- second that 800, alcoholysis degree is 99.8 (mol/mol)
The poly- 3- hydroxyl that 60 kilograms of enol powder and the equal particle diameters of number are 0.1mm, volume crystallinity is 50, weight average molecular weight is 90,000
40 kilograms of base butyrate (p-3hb) powder carries out first time physical mixed in homogenizer, and mixing temperature is room temperature, the time
For 3～5 minutes；It is subsequently adding 1.5 kilograms of water, carries out second physical mixed, mixing temperature is room temperature, the time is 3～5 points
Clock；Compound is vacuum dried 6 hours at 100 DEG C, removes excessive moisture；Dried compound is injected screw slenderness ratio
For, in 10 conical double screw extruder, melt extruding at 185 DEG C, it is 8 that adjustment screw speed makes the melting time of compound
Minute；By melt extrusion natural cooling in atmosphere, pelletizer, prepare milky, the graininess of smooth surface is gathered
Vinyl alcohol composite master batch.Through capillary rheometer determining, this masterbatch temperature be 185 DEG C, shear rate be 100,1000,
10000s-1Under apparent shear viscosity be respectively 9200,3360,475pa s, there is good thermoplastic processability.
Above-described embodiment is not the restriction for the present invention, and the present invention is not limited only to above-described embodiment, as long as meeting
Application claims, belong to protection scope of the present invention.
Claims (5)
1. a kind of polyvinyl alcohol composite master batch, is blend it is characterised in that this blend includes polyvinyl alcohol, poly- hydroxy aliphatic
Acid esters；The weight content of wherein polyvinyl alcohol is 51～99, and the weight content of polyhydroxyalkanoate is 1～49,175
～185 DEG C, 100s-1Under conditions of shear rate, the apparent shear viscosity of polyvinyl alcohol composite master batch is less than 20000pa s；
The average degree of polymerization of polyvinyl alcohol is 600～1800, and alcoholysis degree is 88～99.8, and unit is mol/mol；
Polyhydroxyalkanoate has a following chemical structure of general formula:
R in formula1For h, m1 be 2, x be 200～20000 random natural number, y be 0 when polyhydroxyalkanoate be poly- 4- hydroxyl
Base butyrate, its equal particle diameter of number is 0.01～0.1mm, and volume crystallinity is 30～70, weight average molecular weight is 9～65
Ten thousand；
R in formula1For ethyl c2h5, m1 be 1, x be 200～20000 random natural number, y be 0 when polyhydroxyalkanoate
For poly- 3- hydroxyl valerate, its equal particle diameter of number is 0.01～0.1mm, and volume crystallinity is 15～55, weight average molecular weight
For 9～650,000；
R in formula1For methyl ch3、r2For h, m1 be 1, m2 be 2, x and y be 200～20000 random natural number when poly- hydroxyl
Base fatty acid ester is poly- 3-hydroxybutyrate -4 hydroxybutyric acid copolyesters, and its equal particle diameter of number is 0.01～0.1mm, and volume is tied
Brilliant degree is 10～50, weight average molecular weight is 9～750,000, and the molar content of 4 hydroxybutyric acid ester therein is 1～45；
R in formula1For methyl ch3、r2For ethyl c2h5, m1 and m2 be the random natural number that 1, x and y is 200～20000
When polyhydroxyalkanoate be poly butyric-valeric acid copolyesters, its number equal particle diameters be 0.01～0.1mm, volume crystallization
Spending for 15～65, weight average molecular weight is 9～750,000, and the molar content of 3- hydroxyl valerate therein is 1～45.
2. as claimed in claim 1 a kind of polyvinyl alcohol composite master batch it is characterised in that poly- second in polyvinyl alcohol composite master batch
The weight content of enol is 60～90, and the weight content of polyhydroxyalkanoate is 10～40,175～185 DEG C,
100s-1Under conditions of shear rate, the apparent shear viscosity of polyvinyl alcohol composite master batch is less than 10000pa s；
The average degree of polymerization of polyvinyl alcohol is 600～1000, and alcoholysis degree is 88～99.8, and unit is mol/mol.
3. preparation as claimed in claim 1 a kind of method of polyvinyl alcohol composite master batch it is characterised in that the method include with
Lower step:
Step (1). pva powder and polyhydroxyalkanoate powder are carried out first time physical mixed uniformly, is subsequently adding
Deionized water carries out second physical mixed, obtains compound after mix homogeneously；Wherein polyvinyl alcohol and polyhydroxyalkanoate
Weight ratio for 51:49～99:1, the weight of deionized water is polyvinyl alcohol with the 0.5 of polyhydroxyalkanoate gross weight～
1.5；
The equal particle diameter of number of described polyvinyl alcohol is 0.01～0.1mm, and average degree of polymerization is 600～1800, and alcoholysis degree is
88～99.8, unit is mol/mol；
Described polyhydroxyalkanoate has a following chemical structure of general formula:
R in formula1For h, m1 be 2, x be 200～20000 random natural number, y be 0 when polyhydroxyalkanoate be poly- 4- hydroxyl
Base butyrate, its equal particle diameter of number is 0.01～0.1mm, and volume crystallinity is 30～70, weight average molecular weight is 9～65
Ten thousand；
R in formula1For ethyl c2h5, m1 be 1, x be 200～20000 random natural number, y be 0 when polyhydroxyalkanoate
For poly- 3- hydroxyl valerate, its equal particle diameter of number is 0.01～0.1mm, and volume crystallinity is 15～55, weight average molecular weight
For 9～650,000；
R in formula1For methyl ch3、r2For h, m1 be 1, m2 be 2, x and y be 200～20000 random natural number when poly- hydroxyl
Base fatty acid ester is poly- 3-hydroxybutyrate -4 hydroxybutyric acid copolyesters, and its equal particle diameter of number is 0.01～0.1mm, and volume is tied
Brilliant degree is 10～50, weight average molecular weight is 9～750,000, and the molar content of 4 hydroxybutyric acid ester therein is 1～45；
R in formula1For methyl ch3、r2For ethyl c2h5, m1 and m2 be the random natural number that 1, x and y is 200～20000
When polyhydroxyalkanoate be poly butyric-valeric acid copolyesters, its number equal particle diameters be 0.01～0.1mm, volume crystallization
Spending for 15～65, weight average molecular weight is 9～750,000, and the molar content of 3- hydroxyl valerate therein is 1～45；
Step (2). it is constant that the compound obtaining step (1) is dried under vacuum to constant weight in 60～100 DEG C, removes superfluous water
Point；
Step (3). the injection of dried for step (2) compound is carried in the screw extruder of heater, the major diameter of screw rod
Ratio for 10～30, melts 4～8 minutes at 175～185 DEG C, melt extrudes and obtain melt extrusion；
Step (4). step (3) melt extrusion is naturally cooled to room temperature, pelletizer in atmosphere, prepares and can be used for
The particulate polyethylene alcohol composite master batch of thermoplastic processing.
4. as claimed in claim 3 a kind of preparation method of polyvinyl alcohol composite master batch it is characterised in that polyvinyl alcohol with poly-
The weight of hydroxy fatty acid is than for 6:4～9:1.
5. as claimed in claim 3 a kind of preparation method of polyvinyl alcohol composite master batch it is characterised in that the number of polyvinyl alcohol
All particle diameter is 0.01～0.055mm, and average degree of polymerization is 600～1000, and alcoholysis degree is 88～99.8, and unit is
mol/mol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140344.2A CN103951919B (en) | 2014-04-09 | 2014-04-09 | Polyvinyl alcohol composite master batch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410140344.2A CN103951919B (en) | 2014-04-09 | 2014-04-09 | Polyvinyl alcohol composite master batch and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951919A CN103951919A (en) | 2014-07-30 |
| CN103951919B true CN103951919B (en) | 2017-02-01 |
Family
ID=51329286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410140344.2A Active CN103951919B (en) | 2014-04-09 | 2014-04-09 | Polyvinyl alcohol composite master batch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951919B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371290B (en) * | 2014-11-14 | 2016-08-17 | 林煜茂 | A kind of environment-friendly type compound bio macromolecular material and preparation method thereof |
| CN109517308B (en) * | 2018-10-31 | 2021-07-16 | 中国石油化工股份有限公司 | Polyvinyl alcohol melt for polaroid and preparation method of film thereof |
| CN109370130B (en) * | 2018-10-31 | 2021-07-02 | 中国石油化工股份有限公司 | Preparation method of high-concentration low-viscosity polyvinyl alcohol melt and film thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1444445A (en) * | 2000-06-09 | 2003-09-24 | 宝洁公司 | Agricultural items and methods comprising biodegradable copolymers |
| CN103205076A (en) * | 2013-04-15 | 2013-07-17 | 四川大学 | Thermoplastic polyvinyl alcohol-polylactic acid blending material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3345084B2 (en) * | 1993-04-01 | 2002-11-18 | 株式会社クラレ | Polyvinyl alcohol resin composition |
-
2014
- 2014-04-09 CN CN201410140344.2A patent/CN103951919B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1444445A (en) * | 2000-06-09 | 2003-09-24 | 宝洁公司 | Agricultural items and methods comprising biodegradable copolymers |
| CN103205076A (en) * | 2013-04-15 | 2013-07-17 | 四川大学 | Thermoplastic polyvinyl alcohol-polylactic acid blending material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "聚乙二醇改性的热塑性淀粉的结构与性能";汪劲波等;《化学工业与工程技术》;20060430;第27卷(第2期);第20-23页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951919A (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107540920B (en) | Metallocene polyethylene composition and preparation method thereof | |
| CN1073457A (en) | Produce the method for plasticised polyvinyl alcohol and be used to prepare the thermoplastic compounds of starch-based, biodegradable | |
| CN104072881A (en) | Thermoplastic micro-foaming damping material and preparation method thereof | |
| CN107936430A (en) | High fluidity polyvinyl alcohol that thermoplastification is modified, cast film materials and preparation method thereof | |
| CN102529056B (en) | Preparation method for high melt strength poly lactic acid, and extruder thereof | |
| CN102532664A (en) | Silane cross-linked polyethylene insulating material and production method thereof | |
| CN105670191A (en) | Special material for modified starch-polyvinyl alcohol degradable membrane | |
| CN107936431A (en) | Polyvinyl alcohol water solubility casting films and preparation method thereof | |
| CN103113653B (en) | HDPE (high-density polyethylene)/LDPE (low-density polyethylene) blended foam material and preparation method thereof | |
| CN103951919B (en) | Polyvinyl alcohol composite master batch and preparation method thereof | |
| CN108929527A (en) | A kind of PBAT/ modified starch full-biodegradable film and its preparation method and application having both high ductibility and high obstructing performance | |
| CN104371296A (en) | Poly-methyl ethylene carbonate composition and preparation method thereof | |
| CN101851378A (en) | Extrusion grade ASA resin with easy processing and high apparent property and preparation method thereof | |
| CN104262915A (en) | Method for preparing low-mobility polylactic-acid-base plasticizing wood-plastic composite material | |
| CN106554553B (en) | Easy processing metallocene PE composition and preparation method thereof | |
| CN110698746A (en) | Polyethylene foam and preparation method thereof | |
| CN106905676A (en) | A kind of preparation method of PLA polypropylene alloy expanded material | |
| CN111205605A (en) | High-melt-strength polyhydroxyalkanoate blend and film, and preparation method and application thereof | |
| CN112708230B (en) | Thermoplastic polyvinyl alcohol composition with special surface property, film and preparation method thereof | |
| CN107556675A (en) | A kind of polyvinyl alcohol water solubility 3D printing support consumptive material and preparation method thereof | |
| CN103408907A (en) | Modified polylactic resin particles and application thereof | |
| CN110016213A (en) | A kind of polylactic acid foam material and preparation method thereof with micro-nano compound abscess | |
| CN102875987B (en) | A kind of organic nucleating agent and its preparation and application | |
| CN111087766A (en) | Thermoplastic blend material, blend thermoplastic film and preparation method thereof | |
| CN107540935B (en) | Polypropylene reclaimed material composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |