CN107627527A - The preparation method of copolymerized polymer foam with hydrophilic units - Google Patents
The preparation method of copolymerized polymer foam with hydrophilic units Download PDFInfo
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- CN107627527A CN107627527A CN201710923555.7A CN201710923555A CN107627527A CN 107627527 A CN107627527 A CN 107627527A CN 201710923555 A CN201710923555 A CN 201710923555A CN 107627527 A CN107627527 A CN 107627527A
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Abstract
The preparation method of copolymerized polymer foam with hydrophilic units, belongs to foam technology field.Solve in existing foamed material preparation technology, foam inside is difficult to the technical barrier of timely cooling and shaping.The method of the present invention, it is before foaming is processed, first the copolymerized polymer of the hydrophilic structure unit containing 0.2wt% 40wt% is granulated or is further processed into moulded from foam module, obtains copolymerized polymer to be foamed；Then copolymerized polymer to be foamed is first subjected to water suction processing before foaming is processed, then foamed, obtain copolymerized polymer foam, or, copolymerized polymer to be foamed is subjected to water suction processing while foaming and processing, obtains copolymerized polymer foam.This method, using water as internal coolant, process is green, and safety and stability, cost is cheap, can produce thicker foamed material, and the foamed material quality prepared is more stable.
Description
Technical field
The invention belongs to foam technology field, and in particular to a kind of copolymerized polymer foam with hydrophilic units
Preparation method.
Background technology
Foamed material is as a kind of foamed material using gas as filler, not only light weight, and material saving, specific strength is high, and
And with performances such as excellent heat-insulated, sound insulation, bufferings.Foamed material is widely used in industry, agricultural, communications and transportation, motion
The field such as equipment and Aero-Space.Many polymer can be used to manufacture foamed material, wherein polystyrene foam, polyurethane
Foam, polyethylene, polyvinyl chloride foam and sponge rubber foam are to apply wide foamed material kind.And some are tied
The polymer of crystalline substance, such as PP, nylon, polyester, melt strength declines rapidly after melting due to them, makes their foaming process
Often it is difficult to control, improves their production difficulty, limits their application.
The production method of plastic foam is varied, wherein the preparation method of the most commonly used foamed material has：Autoclave is sent out
Bubble, moulded from foam, extrusion foaming and injection foaming etc..Although the equipment and specific operation process of these foaming methods are poor
It is different, but the general principle of its bubble growth is all similar：First stage, foaming agent are dispersed into resin matrix；Second-order
Section, by the induction of temperature and pressure, bubble nucleating and grow form foam of polymers；Phase III, foam of polymers cooling
Sizing obtains foam product.Improvement and research in terms of many foam productions are all based on principle above.
People have found in production practices, larger foam material material are being prepared, especially with moulded from foam or extrusion
During foam process, often there is phenomena such as inside and outside aperture difference is big, and core is shown and hole, melting collapse, discoloration in foam.This is
Because after the completion of foaming second stage, polymer has formed foaming structure, and thermal conductivity factor declines, although close to cuticle region
Foam be easier to cooling sizing, but be difficult to be passed away away from the core area heat of epidermis, it is impossible to realize rapid cooling
Sizing, and change colour, abscess merges, melts phenomena such as collapsing.For the moulded from foam, extrusion foaming and note of many polymer
Foam process is moulded, due to being difficult to solve the technical barrier of quick cooling and shaping inside phase III foam of polymers, so often
Relatively thin foamed material can only be produced.During as needed thicker product, then need multi-layer bonded by being carried out to the small product of thickness
To realize, cost is not only improved, and influence product quality.
We have found by theoretical modeling and substantial amounts of experimental verification, are sent out for polymer of the blowing temperature higher than 100 DEG C
Bubble technique, before foaming, a certain amount of moisture is contained in polymeric material, during foaming, these moisture will vaporize simultaneously
Substantial amounts of latent heat of phase change is absorbed, makes the temperature of foam inside reduce rapidly, has the function that foam cooling and shaping, prevents foaming
The phenomenon that abscess caused by the cooling not in time of three stages and hole, melting collapse or even changed colour.This production to foam has very
Important practical significance.
The content of the invention
In view of this, the present invention provides a kind of preparation method of the copolymerized polymer foam with hydrophilic units.
Present invention aim to address in existing foam technology technique, the technology that foam inside is difficult to timely cooling and shaping is difficult
Topic, i.e.,：The difficult technical barrier of polymer foaming cooling and shaping stage internal cooling, there is provided a kind of using in copolymerized polymer
Hydrophilic radical is absorbed water before foaming or in foaming process, is then former inside foam is carried out in foaming latter stage using these water
The foaming new method of position cooling.
It is as follows that the present invention solves the technical scheme that above-mentioned technical problem is taken：
The preparation method of copolymerized polymer foam with hydrophilic units：
(1) before foaming is processed, the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% is granulated,
Obtain copolymerized polymer to be foamed；
Or, before foaming is processed, be first granulated the co-polymeric of the hydrophilic structure unit containing 0.2wt%-40wt%,
Moulded from foam module is subsequently processed into, obtains copolymerized polymer to be foamed；
Or, foaming process before, first by the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% with
CBA melting mixing is simultaneously processed into moulded from foam module, obtains copolymerized polymer to be foamed；
(2) copolymerized polymer to be foamed first carries out water suction processing before foaming is processed, then foams, and obtains copolymerized polymer
Foam, or, the copolymerized polymer to be foamed carries out water suction processing while foaming and processing, and obtains copolymerized polymer foam；
It in step (2), if copolymerized polymer to be foamed does not contain CBA, need to be foamed, be sent out using foaming agent
Infusion is physical blowing agent or CBA；
The copolymerized polymer be below blowing temperature, do not chemically reacted with water, and can use extrusion foaming,
One or more methods prepare thermoplastic co-polymer's fluoropolymer resin of foamed material in moulded from foam, injection foaming；
The quality for the water that copolymerized polymer to be foamed absorbs is the 0.5-30% of co-polymeric amount of substance to be foamed.
Preferably, the process of step (2) is as follows：
(21) copolymerized polymer to be foamed is put into closed container, and adds water logging and do not have co-polymeric to be foamed
Thing, container inner pressure is improved to 0.5MPa-10MPa, temperature keeps temperature and pressure decentralization to set to 0 .5-24h to 80-170 DEG C
Afterwards, temperature in container is reduced, to 0-40 DEG C, pressure release, to take out, obtain the copolymerized polymer to be foamed of pre- water suction；
(22) if copolymerized polymer to be foamed is graininess, the copolymerized polymer and foaming agent to be foamed that absorb water in advance are added
The melting mixing into extrusion foaming equipment or injection foaming equipment, obtained melt is in extrusion foaming machine die orifice or injection foaming machine
Foaming in mold cavity, obtain copolymerized polymer foam；
If copolymerized polymer to be foamed is module shape and is free of CBA, the copolymerized polymer to be foamed that will be absorbed water in advance
It is put into moulded from foam mould, and physical blowing agent is added into mould, heat, keeps pressurization, treat that physical blowing agent is immersed in
In copolymerized polymer module to be foamed, die sinking foaming, copolymerized polymer foam is obtained；
If copolymerized polymer to be foamed is module shape and contains CBA, the copolymerized polymer to be foamed to absorb water in advance is put
Enter in moulded from foam mould, temperature-pressure, die sinking foaming, obtain copolymerized polymer foam.
Preferably, the process of step (2) is as follows：
If copolymerized polymer to be foamed is graininess, copolymerized polymer to be foamed, foaming agent and water are added to extrusion hair
Melting mixing in bubble or injection foaming equipment, the quality for adding water is the 0.5-30% of co-polymeric amount of substance to be foamed, then
By the copolymerized polymer melt to be foamed with water and foaming agent in extrusion foaming machine die orifice or injection foaming machine mold cavity
Foaming, obtain copolymerized polymer foam；
The foaming agent is physical blowing agent or CBA；
If copolymerized polymer to be foamed is module shape and is free of CBA, copolymerized polymer to be foamed is put into molding
In foaming mould, and water is added, copolymerized polymer to be foamed is completely submerged in water, physical blowing agent is added into mould,
Heating, pressurization is kept, in equilibrium process, foaming agent and water are immersed in copolymerized polymer module to be foamed, are obtained containing water
Copolymerized polymer module to be foamed, die sinking foaming, obtain copolymerized polymer foam；
If copolymerized polymer to be foamed is module shape and contains CBA, copolymerized polymer to be foamed is put into molding hair
Steep in mould, and add water, copolymerized polymer to be foamed is completely submerged in water, temperature-pressure, in equilibrium process, water logging
Enter into copolymerized polymer module to be foamed, obtain the copolymerized polymer module to be foamed containing water, die sinking foaming, be copolymerized
Foam of polymers.
Further, the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% is replaced with into composite wood
Material, composite do not chemically react below blowing temperature, with water, and can use extrusion foaming, moulded from foam, injection
One or more methods prepare foamed material in foaming, contain 0.2wt%-40wt% hydrophilic structure units in composite
The content of copolymerized polymer is no less than 40wt%.
Preferably, the copolymerized polymer containing 0.2wt%-40wt% hydrophilic structure units is polypropylene-polyoxy
The grafting of the graft polymers of vinethene, the graft polymers of polyethylene-polyoxyethylene ether, polystyrene-polyoxyethylene ether gathers
Compound, the graft polymers of polyvinyl chloride-APEO, the block polymer of polypropylene-APEO, polyethylene-poly-
The block polymer of oxygen vinethene, the block polymer of polystyrene-polyoxyethylene ether, polyvinyl chloride-APEO it is embedding
Section polymer, ethene-vinyl acetate polymer, polyacrylic maleic acid grafted polymers, the grafting of polyacrylic maleic anhydride are poly-
The maleic anhydride grafting of compound, polyacrylic maleate graft polymers, the maleic acid grafted polymers of polyethylene, polyethylene
Polymer, the maleate graft polymers of polyethylene, the maleic acid grafted polymers of polystyrene, the maleic acid of polystyrene
Acid anhydride graft polymers, the maleate graft polymers of polystyrene, the maleic acid grafted polymers of polyvinyl chloride, polyvinyl chloride
Maleic anhydride grafted polymer, the maleate graft polymers of polyvinyl chloride, polyacrylic acrylic acid graft polymer, poly-
The graft polymerization of acrylic ester thing of propylene, the acrylic acid graft polymer of polyethylene, polyethylene graft polymerization of acrylic ester thing,
The acrylic acid graft polymer of polystyrene, the graft polymerization of acrylic ester thing of polystyrene, polyvinyl chloride it is acrylic acid-grafted
Polymer, the graft polymerization of acrylic ester thing of polyvinyl chloride, polyacrylic methacrylic acid graft polymers, polyacrylic methyl
Graft polymerization of acrylic ester thing, the methacrylic acid graft polymers of polyethylene, the methacrylate of polyethylene are graft-polymerized
Thing, the methacrylic acid graft polymers of polystyrene, the methacrylate graft polymers of polystyrene, polyvinyl chloride
Methacrylic acid graft polymers, the methacrylate graft polymers of polyvinyl chloride, the polymerization of polyacrylic Itaconic Acid Grafted
Thing, polyacrylic itaconate graft polymers, the Itaconic Acid Grafted polymer of polyethylene, the itaconate grafting of polyethylene are poly-
Compound, the Itaconic Acid Grafted polymer of polystyrene, the itaconate graft polymers of polystyrene, the itaconic acid of polyvinyl chloride
Graft polymers, the itaconate graft polymers of polyvinyl chloride, polyacrylic fumaric acid graft polymers, polyacrylic rich horse
Acid esters graft polymers, the fumaric acid graft polymers of polyethylene, the fumarate graft polymers of polyethylene, polystyrene
Fumaric acid graft polymers, the fumarate graft polymers of polystyrene, the fumaric acid graft polymers of polyvinyl chloride, polychlorostyrene
The fumarate graft polymers of ethene, polyacrylic starch graft copolymers, the starch graft copolymers of polyethylene, polyphenyl second
One or more in the starch graft copolymers of alkene, the starch graft copolymers of polyvinyl chloride.
Preferably, in the copolymerized polymer to be foamed, the mass fraction of hydrophilic structure unit is 1wt%-30wt%.
Preferably, the CBA be sodium acid carbonate, ammonium carbonate, N, N- dinitrosopentamethlyene tetramines, N, N-
Bis- sub- terephthalate amine of dimethyl-N, N-, azodicarbonamide, azodiisobutyronitrile, azoformic acid isopropyl ester, azo diformazan
Diethyl phthalate, two azoaminobenzenes, Barium azodicarboxylate, 4,4 ,-disulfonyl hydrazide diphenyl ether, to benzene sulfonyl hydrazide, 3,3- disulfonyls
Hydrazine diphenyl sulphone (DPS), 4,4, the one or more in-two benzene disulfohydrazides, benzen 1,3 disulphonyl hydrazide, 1,4- benzene disulfohydrazides.
Preferably, the physical blowing agent is carbon dioxide, nitrogen, air, argon gas, methane, ethane, propane, butane, penta
One or more in alkane.
Preferably, before step 1 is granulated or/and during step 2 melting mixing, by bubble nucleating agent, antioxidant, resist
One or more in electrostatic agent, antiseptic, plasticizer, lubricant, brightener, conductive auxiliary agent, crystal controlling agent fuse into body
In system.
The present invention principle be：Utilize the water absorbing capacity of the hydrophilic units in the copolymerized polymer with hydrophilic units
Power, before foaming processing or in foaming process, the method by heating immersion, introduce a certain amount of water, material in the material in advance
Material is when temperature and pressure is induced and foamed, water rapid vaporization under blowing temperature, and absorbs a large amount of latent heats of phase change, foam inside temperature
Degree is reduced rapidly, realizes the effect of cooling sizing.
Compared with prior art, beneficial effects of the present invention are：
The method of the copolymerized polymer foam with hydrophilic units of the present invention, using water as internal coolant, solve
During polymer foaming, the inside and outside foam aperture difference that foam inside is difficult to caused by cooling sizing in time is big, inside bubble
Foam changes colour, inner cell and hole is serious, the problem of inner foam layer collapses, therefore foamed material quality prepared by the method for the present invention
It is more stable, thickness can be produced and reach 30cm, or even more than 30cm foamed material；
The method of the copolymerized polymer foam with hydrophilic units of the present invention, using water as internal coolant, green
Environmental protection, safety and stability, cost are cheap.
Embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched with reference to embodiment
State, but it is to be understood that these descriptions are simply for further explanation the features and advantages of the present invention rather than to patent of the present invention
It is required that limitation.
The preparation method of the copolymerized polymer foam with hydrophilic units of the present invention：
(1) before foaming is processed, the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% is granulated,
Obtain copolymerized polymer to be foamed；
Or, before foaming is processed, be first granulated the co-polymeric of the hydrophilic structure unit containing 0.2wt%-40wt%,
Moulded from foam module is subsequently processed into, obtains copolymerized polymer to be foamed；
Or, foaming process before, first by the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% with
CBA melting mixing is simultaneously processed into moulded from foam module, obtains copolymerized polymer to be foamed；
Wherein, it is granulated generally use extruding pelletization；Melting mixing is method well known in the art, can be banbury
Melt mixing methods, single screw rod mixing method or double-screw mixing are legal, but it is several to be not limited to the above；It is processed into moulded from foam module
Method is method well known in the art, can be injection molding, extrusion molding, compression molding etc.；CBA adds
It is those skilled in the art's common dose to enter amount, and usual CBA accounts for the 0.2-10wt% of copolymerized polymer to be foamed.
(2) pre-absorption quality is copolymerization to be foamed before copolymerized polymer to be foamed foaming processing or in foaming process
The 0.5-30% of polymer quality moisture content, foaming is then induced to produce abscess again.
As one of implementation, the copolymerized polymer to be foamed first carries out water suction processing before foaming is processed, then foams,
The copolymerized polymer to be foamed of pre- water suction is obtained, process is as follows：
(21) copolymerized polymer to be foamed is put into closed autoclave, and adds water logging and do not have co-polymeric to be foamed
Thing, close autoclave valve, improve autoclave in pressure to 0.5MPa-10MPa, temperature to 80-170 DEG C, keep the temperature and
After pressure decentralization sets to 0 .5-24h, high pressure temperature in the kettle is reduced to 0-40 DEG C, pressure release, takes out, obtains the copolymerization to be foamed of pre- water suction
Polymer, the water absorption of the copolymerized polymer to be foamed to absorb water in advance are the 0.5-30% of co-polymeric amount of substance to be foamed；
(22) if copolymerized polymer to be foamed is graininess, the copolymerized polymer and foaming agent to be foamed that absorb water in advance are added
Into extrusion foaming equipment or injection foaming equipment, melting mixing, obtained melt is in extrusion foaming machine die orifice or injection foaming
Foaming in machine mold cavity, obtain copolymerized polymer foam；
Wherein, foaming agent is physical blowing agent or CBA, and the addition of foaming agent is normal for those skilled in the art
With dosage, the addition of usual foaming agent is the 0.2-10% of the co-polymeric amount of substance to be foamed to absorb water in advance, extrusion foaming machine
Or injection foaming 130-220 DEG C of temperature of machining；
If copolymerized polymer to be foamed is module shape and is free of CBA, the copolymerized polymer to be foamed that will be absorbed water in advance
It is put into moulded from foam mould, and physical blowing agent is added into mould, is heated up to 130-220 DEG C, holding pressure is 0.5-
20MPa, 1-10h being permeated, physical blowing agent is immersed in copolymerized polymer module to be foamed, reaches osmotic equilibrium, and die sinking is foamed,
Obtain copolymerized polymer foam；
Wherein, the addition of physical blowing agent is determined by pressure, i.e., at the required temperatures, pressure is guarantee system
0.5-20MPa；
If copolymerized polymer to be foamed is module shape and contains CBA, the copolymerized polymer to be foamed to absorb water in advance is put
Enter in moulded from foam mould, be heated up to 130-220 DEG C, be forced into 0.5-20MPa, be incubated 0.2-10h, die sinking foaming, be total to
Poly polymer foam.
In above-mentioned extrusion foaming, injection foaming, moulded from foam technique, the copolymerized polymer to be foamed that absorbs water in advance, nothing
By being particle or module, internal cooling effect is respectively provided with.
As another implementation, the copolymerized polymer to be foamed carries out water suction processing while foaming and processing, and obtains
Copolymerized polymer foam, process are as follows：
If copolymerized polymer to be foamed is graininess, copolymerized polymer to be foamed, foaming agent and water are added to extrusion hair
Melting mixing in equipment or injection foaming equipment is steeped, the quality for adding water is the 0.5-30% of co-polymeric amount of substance to be foamed,
Then by the copolymerized polymer melt to be foamed with water and foaming agent in extrusion foaming machine die orifice or injection foaming machine mould type
Intracavitary foaming, obtain copolymerized polymer foam；
Wherein, foaming agent is physical blowing agent or CBA, and the addition of foaming agent is normal for those skilled in the art
With dosage, the addition of usual foaming agent is the 0.2-10% of co-polymeric amount of substance to be foamed, extrusion foaming machine or injection hair
Bubble 130-220 DEG C of temperature of machining；
In above-mentioned extrusion foaming, injection foaming technique, co-polymeric composition granule to be foamed absorbs in process
Moisture, forms the copolymerized polymer melten gel to be foamed with moisture, and moisture plays internal cooling effect in foaming process.
If copolymerized polymer to be foamed is module shape and is free of CBA, copolymerized polymer to be foamed is put into molding
In foaming mould, and water is added, copolymerized polymer to be foamed is completely submerged in water, physical blowing agent is added into mould,
130-220 DEG C is heated up to, holding pressure is 0.5-20MPa, permeates 1-10h, foaming agent and water are immersed in co-polymeric to be foamed
In thing module, reach osmotic equilibrium, obtain the copolymerized polymer module to be foamed containing water, die sinking foaming, obtain co-polymeric
Thing foam；
Wherein, the addition of physical blowing agent is determined by pressure, i.e., at the required temperatures, pressure is guarantee system
0.5-20MPa。
In above-mentioned moulded from foam technique, copolymerized polymer to be foamed absorbs moisture in process, has inside
Cooling effect.
If copolymerized polymer to be foamed is module shape and contains CBA, copolymerized polymer to be foamed is put into molding hair
Steep in mould, and add water, copolymerized polymer to be foamed is completely submerged in water, be heated up to 130-220 DEG C, be forced into 0.5-
20MPa, is incubated 1-10h, and water is immersed in copolymerized polymer module to be foamed, reaches osmotic equilibrium, obtain containing the pending of water
Copolymerized polymer module is steeped, die sinking foaming, obtains copolymerized polymer foam；
In above-mentioned moulded from foam technique, copolymerized polymer module to be foamed absorbs moisture in process, has
Internal cooling effect.
In the present invention, it is in foaming temperature that the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt%, which is granulated,
Below degree, do not chemically react, and can use one or more in extrusion foaming, moulded from foam, injection foaming with water
Method prepares thermoplastic co-polymer's polymer of foamed material.The mass fraction of preferred hydrophilic construction unit is 1wt%-
30wt%.
The co-polymeric resin containing 0.2wt%-40wt% hydrophilic structure units of the present invention, can also be replaced with
Composite.Composite does not chemically react below blowing temperature, with water, and can use extrusion foaming, molding hair
One or more methods prepare foamed material in bubble, injection foaming, and composite is by containing 0.2wt%-40wt% hydrophily knots
The copolymerized polymer of structure unit forms with additive and/or other polymers resin, and contains hydrophilic structure in composite
Ratio shared by the COPP of unit is no less than 40wt%；Preferably, other polymers resin is polypropylene, polyethylene, gathered
One or more in styrene, polyvinyl chloride, polyethylene octene copolymer, PLA.
In the present invention, the co-polymeric resin containing 0.2wt%-40wt% hydrophilic structure units is polypropylene-poly-
The grafting of the graft polymers of oxygen vinethene, the graft polymers of polyethylene-polyoxyethylene ether, polystyrene-polyoxyethylene ether
Polymer, the graft polymers of polyvinyl chloride-APEO, the block polymer of polypropylene-APEO, polyethylene-
The block polymer of APEO, the block polymer of polystyrene-polyoxyethylene ether, polyvinyl chloride-APEO
Block polymer, ethene-vinyl acetate polymer, polyacrylic maleic acid grafted polymers, the grafting of polyacrylic maleic anhydride
Polymer, polyacrylic maleate graft polymers, the maleic acid grafted polymers of polyethylene, the maleic anhydride of polyethylene connect
Branch polymer, the maleate graft polymers of polyethylene, the maleic acid grafted polymers of polystyrene, the Malaysia of polystyrene
Anhydride-grafted polymers, the maleate graft polymers of polystyrene, the maleic acid grafted polymers of polyvinyl chloride, polychlorostyrene second
The maleic anhydride grafted polymer of alkene, the maleate graft polymers of polyvinyl chloride, polyacrylic acrylic acid graft polymer,
Polyacrylic graft polymerization of acrylic ester thing, the acrylic acid graft polymer of polyethylene, the graft polymerization of acrylic ester of polyethylene
Thing, the acrylic acid graft polymer of polystyrene, the graft polymerization of acrylic ester thing of polystyrene, the acrylic acid of polyvinyl chloride connect
Branch polymer, the graft polymerization of acrylic ester thing of polyvinyl chloride, polyacrylic methacrylic acid graft polymers, polyacrylic first
Base graft polymerization of acrylic ester thing, the methacrylic acid graft polymers of polyethylene, the methacrylate grafting of polyethylene are poly-
Compound, the methacrylic acid graft polymers of polystyrene, methacrylate graft polymers, the polyvinyl chloride of polystyrene
Methacrylic acid graft polymers, methacrylate graft polymers, the polyacrylic Itaconic Acid Grafted of polyvinyl chloride gather
The itaconate grafting of compound, polyacrylic itaconate graft polymers, the Itaconic Acid Grafted polymer of polyethylene, polyethylene
Polymer, the Itaconic Acid Grafted polymer of polystyrene, the itaconate graft polymers of polystyrene, the clothing health of polyvinyl chloride
Sour graft polymers, the itaconate graft polymers of polyvinyl chloride, polyacrylic fumaric acid graft polymers, polyacrylic richness
Fumaric ester graft polymers, the fumaric acid graft polymers of polyethylene, fumarate graft polymers, the polystyrene of polyethylene
Fumaric acid graft polymers, the fumarate graft polymers of polystyrene, the fumaric acid graft polymers, poly- of polyvinyl chloride
Fumarate graft polymers, polyacrylic starch graft copolymers, the starch graft copolymers of polyethylene, the polyphenyl of vinyl chloride
One or more mixing in any proportion in the starch graft copolymers of ethene, the starch graft copolymers of polyvinyl chloride.
The copolymerized polymer with hydrophilic structure unit of the present invention, be not limited to it is foregoing several, it is all to carry hydrophilic structure
The copolymerized polymer not reacted below unit and blowing temperature with water, it is used equally for patent to reach water suction cooling foaming in situ and sets
The effect of fat, belong to scope described in this patent.
In the present invention, the coal addition position of foaming agent, can according to adding foaming agent species and property, selection with it is to be foamed common
Poly polymer is added in extrusion foaming or injection foaming equipment together, can also be selected in extrusion foaming or injection foaming equipment
Melt zone add.In general physical blowing agent adds in extrusion foaming or the melt zone of injection foaming equipment, and chemical blowing
Agent is added to together with copolymerized polymer to be foamed in extrusion foaming or injection foaming equipment.Technical staff can be according to actual foaming
Situation is adjusted.The CBA of the present invention is preferably sodium acid carbonate, ammonium carbonate, N, the methine four of N- dinitrosos five
Amine, N, bis- sub- terephthalate amine of N- dimethyl-N, N-, azodicarbonamide, azodiisobutyronitrile, azoformic acid isopropyl ester,
Diethyl azodiformate, two azoaminobenzenes, Barium azodicarboxylate, 4,4 ,-disulfonyl hydrazide diphenyl ether, to benzene sulfonyl hydrazide, 3,
3- disulfonyl hydrazides diphenyl sulphone (DPS), 4,4 ,-two benzene disulfohydrazides, benzen 1,3 disulphonyl hydrazide, one kind in 1,4- benzene disulfohydrazides or more
Kind.Physical blowing agent be preferably one kind in carbon dioxide, nitrogen, air, argon gas, methane, ethane, propane, butane, pentane or
It is a variety of.
, can also be according to the experience in the industry, in preparation process in order to optimize properties of product or foam performance in the present invention
In, typically before step 1 is granulated or/and during step 2 melting mixing, by bubble nucleating agent, antioxidant, antistatic
One or more in agent, antiseptic, plasticizer, lubricant, brightener, conductive auxiliary agent, crystal controlling agent are fused into system.
The preferred embodiments of the present invention are illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
By polypropylene-APEO graft copolymerization polymer (polyethenoxy ether content 20wt%) in double screw extruder
Middle melt pelletization, obtain co-polymeric composition granule to be foamed；Obtained co-polymeric composition granule to be foamed is fitted into autoclave,
The water for being enough to submerge co-polymeric composition granule to be foamed is added, and is stirred continuously, autoclave temp is increased to 170 DEG C, kettle internal pressure
Power is increased to 0.5MPa, pressurize 0.5h, then reduces autoclave temp to 30 DEG C, rapid pressure release, copolymerized polymer to be foamed
Surface attachment water is sloughed in grain centrifugation, is obtained the co-polymeric composition granule to be foamed of pre- water suction, is detected through thermogravimetry, and absorb water matter
Measure as the 15% of copolymerized polymer granular mass to be foamed；Co-polymeric composition granule to be foamed is added to extrusion foaming equipment
In, carbon dioxide is added as foaming agent in melt zone, and carbon dioxide intake is the copolymerized polymer to be foamed to absorb water in advance
The 3% of grain, melt zone temperature are 220 DEG C, 155 DEG C of head blowing temperature, obtain the thick polypropylene of 1cm-APEO grafting
Copolymerized polymer foamed material.
After testing, polypropylene-APEO graft copolymerization polymer foams density is 55kg/m3, inside and outside foam
Uniform pore diameter, no internal and hole, melts collapse phenomenon.
Embodiment 2
Ethene-vinyl acetate copolymerized polymer (vinyl acetate content 40wt%) is melted in double screw extruder and made
Grain, co-polymeric composition granule is made, then co-polymeric composition granule is fabricated to the to be foamed of 10cm × 15cm × 15cm through injection
Moulded from foam module；Moulded from foam module to be foamed is immersed in the water of moulded from foam mould, foaming kettle is warming up to 140 DEG C,
Being filled with carbon dioxide makes pressure in kettle increase to 5MPa, and pressurize balances 10h, and the moulded from foam module to be foamed in the kettle that foams is completed
Water suction, the absorption of foaming agent carbon dioxide reach balance, then open kettle pressure release, moulded from foam module expansion hair to be foamed rapidly
Bubble, obtains thickness 30cm ethene-vinyl acetate copolymerized polymer foamed material.
After testing, ethene-vinyl acetate copolymerized polymer foam densities are 30kg/m3, uniform pore diameter inside and outside foam,
Without internal and hole, collapse phenomenon is melted.
Embodiment 3
By polyvinyl chloride-starch graft copolymers (content of starch 30wt%), plasticizer DOP and stabilizer organotin according to
Mass ratio 97:2:1 is added in double screw extruder, and melting mixing is granulated, and obtains co-polymeric composition granule to be foamed；Will be to be foamed
Co-polymeric composition granule is added in extrusion foaming equipment, and water and the pressure-air as foaming agent, water are injected into extruder
Addition is the 10% of copolymerized polymer granular mass to be foamed, and air intake is copolymerized polymer granular mass to be foamed
3%, melt zone temperature is 180 DEG C, and head blowing temperature is 160 DEG C, obtains the thick polyvinyl chloride-starch polymer foams of 7cm
Material.
After testing, polyvinyl chloride-starch polymer foam densities are 65kg/m3, uniform pore diameter inside and outside foam, without in
Portion and hole, melt collapse phenomenon.
Embodiment 4
By polystyrene-polypropylene acid graft polymers (polyacrylic acid content 0.5wt%), polyethylene glycol and nucleator carbon
Sour calcium is according to mass ratio 99:0.5:0.5 adds in double screw extruder, and melting mixing is granulated to obtain copolymerized polymer to be foamed
Grain；Obtained co-polymeric composition granule to be foamed is fitted into autoclave, addition is enough to submerge co-polymeric composition granule to be foamed
Water, and be stirred continuously, autoclave temp is increased to 160 DEG C, and being passed through carbon dioxide makes pressure in kettle be increased to 5MPa, pressurize
24h, temperature is then reduced to 30 DEG C, relief valve is opened rapidly, obtains the co-polymeric composition granule to be foamed of pre- water suction, through inspection
Survey, water suction quality is the 2% of copolymerized polymer granular mass to be foamed.The co-polymeric composition granule to be foamed to absorb water in advance is added
In injection foaming machine, high pressure nitrogen is passed through at injection foaming machine melt zone as foaming agent, the quality that nitrogen is filled with is pre-suction
The 2% of the copolymerized polymer granular mass to be foamed of water, 150 DEG C of melting temperature, the co-polymeric composition granule to be foamed to absorb water in advance
Melten gel is expelled in molding foaming mould while foamed, and foam obtains the thick polyphenyl of 10cm by being molded after mould cooling and shaping
Ethylene-polypropylene acid graft polymers foamed material.
After testing, polystyrene-polypropylene acid graft polymers foam densities are 350kg/m3, aperture inside and outside foam
Uniformly, no internal and hole, melts collapse phenomenon.
Embodiment 5
By polyethylene-polyethylene glycol graft polymers (polyethyleneglycol content 5wt%) and azodicarbonamide according to matter
Measure ratio 95:5 melting mixings and the copolymerized polymer moulded from foam module to be foamed that 8cm × 15cm × 15cm is fabricated to through injection；
The moulded from foam module to be foamed is put into closed autoclave, and adds water logging and does not have, closes autoclave valve, improves kettle
To 5MPa, rise temperature in the kettle is kept after absorbing 10h under the temperature and pressure interior pressure to 80 DEG C, reduces temperature in the kettle to 30
DEG C, pressure release, take out, obtain the moulded from foam module to be foamed of pre- water suction, after testing, water suction quality is moulded from foam mould to be foamed
The 8% of block quality.The moulded from foam module to be foamed to absorb water in advance is put into moulded from foam mould, is heated up to 160 DEG C, is sealed,
Pressure is 10MPa, pressurize 5h, and then die sinking foaming, obtains thickness 22cm polyethylene-polyethylene glycol graft polymers foam material
Material.
After testing, polyethylene-polyethylene glycol graft polymers foam densities are 40kg/m3, aperture is equal inside and outside foam
It is even, no internal and hole, melt collapse phenomenon.
Embodiment 6
By the ethylene propylene copolymer of graft polypropylene acid esters, (polyacrylic acid ester content is 8wt%, and ethylene contents are
4wt%), azodicarbonamide and azodiisobutyronitrile in mass ratio 95:2.5:2.5 mixing, are added in extrusion foaming equipment,
10% water of the ethylene propylene copolymer quality of graft polypropylene acid esters, melt zone temperature are added into extrusion foaming machine simultaneously
For 190 DEG C, head blowing temperature is 165 DEG C, obtains the thick polypropylene foams of 1.2cm.
After testing, polypropylene foam density is 60kg/m3, uniform pore diameter inside and outside foam, no internal and hole, melting collapses
Fall into phenomenon.
Embodiment 7
Polystyrene-poly ethylene glycol graft polymers (polyethyleneglycol content 7wt%) is melted in double screw extruder
Melt granulation, co-polymeric composition granule is made, then be molded the copolymerized polymer to be foamed molding for being fabricated to 12cm × 15cm × 15cm
Foam module；The moulded from foam module to be foamed is put into closed autoclave, and adds water logging and does not have, closes autoclave valve
Door, improving pressure in kettle, to 10MPa, rise temperature in the kettle keeps after absorbing 12h under the temperature and pressure to 150 DEG C, reduces kettle
Interior temperature pressure release, is taken out to 0 DEG C, obtains the moulded from foam module to be foamed of pre- water suction, and after testing, water suction quality is to be foamed
The 30% of moulded from foam module quality.The moulded from foam module to be foamed to absorb water in advance is put into moulded from foam mould, is heated up to
180 DEG C, carbon dioxide is filled with as foaming agent, 10MPa, pressurize 5h is forced into, then die sinking foaming, obtains the poly- of thickness 35cm
Styrene-polyethylene glycol graft polymers foamed material.
After testing, polystyrene-poly ethylene glycol graft polymers foam densities are 50kg/m3, aperture inside and outside foam
Uniformly, no internal and hole, melts collapse phenomenon.
Embodiment 8
By ethene-vinyl acetate copolymerized polymer (vinyl acetate content 15wt%) and two azoaminobenzenes in mass ratio
98:2 melting mixings and the moulded from foam module to be foamed that 15cm × 15cm × 15cm is fabricated to through injection；Molding to be foamed is sent out
Bubble module is immersed in the water of moulded from foam mould, and foaming kettle is warming up to 150 DEG C, and being filled with carbon dioxide increases to pressure in kettle
20MPa, 10h is incubated, the moulded from foam module to be foamed in the kettle that foams completes water suction, and the absorption of foaming agent carbon dioxide reaches flat
Weighing apparatus, then opens rapidly kettle pressure release, moulded from foam module to be foamed is expanded foamed, and the ethene-vinyl acetate for obtaining thickness 50cm is total to
Poly polymer foamed material.
After testing, ethene-vinyl acetate copolymerized polymer foam densities are 35kg/m3, uniform pore diameter inside and outside foam,
Without internal and hole, collapse phenomenon is melted.
Embodiment 9
By polypropylene grafted polyacrylate (polyacrylic acid ester content is 3wt%) and PP composite material (polypropylene
Graft polypropylene acid and esters content is 40wt%), and foaming nucleation agent silica in mass ratio 98:2 mixing, use twin-screw extrusion
Agent melt pelletization, then it is then added in extrusion foaming equipment, while the 6% of composite quality is added into extrusion foaming machine
Water, be filled with high pressure nitrogen as foaming agent, the quality that nitrogen is filled with is the copolymerized polymer granular mass to be foamed that absorbs water in advance
2%, melt zone temperature is 190 DEG C, and head blowing temperature is 155 DEG C, obtains the thick polypropylene-based foamed materials of 0.8cm.
After testing, polypropylene-based foam densities are 80kg/m3, uniform pore diameter inside and outside foam, no internal and hole, melting
Collapse phenomenon.
Embodiment 10
By polycthylene grafted APEO (polyethenoxy ether content 8wt%), polyvinyl acetate and conductive black
(wherein polycthylene grafted polyethenoxy ether content is 93%, the conductive black ratio of polyvinyl acetate content 4% to composite
3%) 7cm × 15cm × 15cm moulded from foam module to be foamed, is fabricated to through injection；Moulded from foam module to be foamed is submerged
In the water of moulded from foam mould, foaming kettle is warming up to 130 DEG C, and being filled with carbon dioxide makes pressure in kettle increase to 5MPa, insulation
4h, the moulded from foam module to be foamed in the kettle that foams complete water suction, and the absorption of foaming agent carbon dioxide reaches balance, then rapidly
Kettle pressure release is opened, moulded from foam module to be foamed is expanded foamed, obtains thickness 25cm polyethylene-based copolymerized polymer foamed material.
After testing, polyethylene-based foam densities are 40kg/m3, uniform pore diameter inside and outside foam, no internal and hole, melting
Collapse phenomenon.
Comparative example 1
Acrylic resin is added in extrusion foaming equipment, carbon dioxide is added as foaming agent, dioxy in melt zone
Change 3% that carbon intake is acrylic resin quality, melt zone temperature is 165 DEG C, 155 DEG C of head blowing temperature, polypropylene tree
After fat is expanded foamed at the head, foam occur it is obvious shrink collapse phenomenon, cast aside the discovery of foam section, foam core abscess
Melting is merged into cavity, cannot get good foaming product.
Comparative example 2
Polyvinyl resin is made to 8cm × 10cm × 10cm module, is put into the water of moulded from foam mould, foam kettle liter
For temperature to 170 DEG C, being filled with carbon dioxide makes pressure in kettle increase to 10MPa, pressurize balance 24h, the absorption of foaming agent carbon dioxide
Reach balance, then rapid pressure releasing die sinking, obtain thickness 16cm polyethylene foam material, density 120kg/m3, foam breaks
Face can see, and simultaneously hole and collapse phenomenon are serious for the melting of core abscess.
Comparative example 3
By polyvinyl chloride, plasticizer DOP, stabilizer organotin and azodicarbonamide according to mass ratio 93:3:1:3 add
Into injection foaming agent, 170 DEG C of injection foaming machine melt adhesive temperature, melten gel is expelled in molding foaming mould while foamed, foam
By being molded after mould cooling and shaping, the thick polyvinyl chloride injected foam materials of 10cm are obtained.Polyvinyl chloride foam material density
For 300kg/m3, foam inside discoloration is serious, melting and hole phenomenon occurs.
Illustrated by above-described embodiment 1-10 and comparative example 1-3, the bubble of the copolymerized polymer with hydrophilic unit of the invention
The method of foam, using water as internal coolant, during solving polymer foaming, foam inside is difficult to the institute of cooling sizing in time
Caused inside and outside foam aperture difference is big, internal foam discoloration, inner cell and the problem of hole is serious, and inner foam layer collapses, system
Standby foamed material quality is more stable, can produce thicker foamed material.
Claims (9)
1. the preparation method of the copolymerized polymer foam with hydrophilic units, it is characterised in that
(1) before foaming is processed, the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% is granulated, obtained
Copolymerized polymer to be foamed；
Or, before foaming is processed, first the co-polymeric of the hydrophilic structure unit containing 0.2wt%-40wt% is granulated, then
Moulded from foam module is processed into, obtains copolymerized polymer to be foamed；
Or, before foaming is processed, first by the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% and chemistry
Foaming agent melting mixing is simultaneously processed into moulded from foam module, obtains copolymerized polymer to be foamed；
(2) copolymerized polymer to be foamed first carries out water suction processing before foaming is processed, then foams, and obtains copolymerized polymer bubble
Foam, or, the copolymerized polymer to be foamed carries out water suction processing while foaming and processing, and obtains copolymerized polymer foam；
In step (2), if copolymerized polymer to be foamed does not contain CBA, it need to be foamed using foaming agent, foaming agent
For physical blowing agent or CBA；
The copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% is below blowing temperature, with water not
Chemically react, and one or more methods in extrusion foaming, moulded from foam, injection foaming can be used to prepare foamed material
Thermoplastic co-polymer's fluoropolymer resin；
The quality for the water that copolymerized polymer to be foamed absorbs is the 0.5-30% of co-polymeric amount of substance to be foamed.
2. the preparation method of the copolymerized polymer foam according to claim 1 with hydrophilic units, it is characterised in that
The process of step (2) is as follows：
(21) copolymerized polymer to be foamed is put into closed container, and adds water logging and do not have copolymerized polymer to be foamed, carried
High container inner pressure is to 0.5MPa-10MPa, and temperature is to 80-170 DEG C, after keeping temperature and pressure decentralization to set to 0 .5-24h, drop
Temperature pressure release, is taken out to 0-40 DEG C, obtains the copolymerized polymer to be foamed of pre- water suction in low container；
(22) if copolymerized polymer to be foamed is graininess, the copolymerized polymer and foaming agent to be foamed that absorb water in advance are added to crowded
Go out melting mixing in foaming machine or injection foaming equipment, obtained melt is in extrusion foaming machine die orifice or injection foaming machine mould
Foaming in die cavity, obtain copolymerized polymer foam；
If copolymerized polymer to be foamed is module shape and is free of CBA, the copolymerized polymer to be foamed to absorb water in advance is put into
In moulded from foam mould, and physical blowing agent is added into mould, heated, kept pressurization, it is pending to treat that physical blowing agent is immersed in
Steep in copolymerized polymer module, die sinking foaming, obtain copolymerized polymer foam；
If copolymerized polymer to be foamed is module shape and contains CBA, the copolymerized polymer to be foamed to absorb water in advance is put into mould
In foam mould, temperature-pressure, die sinking foaming, copolymerized polymer foam is obtained.
3. the preparation method of the copolymerized polymer foam according to claim 1 with hydrophilic units, it is characterised in that
The process of step (2) is as follows：
If copolymerized polymer to be foamed is graininess, by copolymerized polymer to be foamed, foaming agent and water be added to extrusion foaming or
Melting mixing in injection foaming equipment, the quality for adding water is the 0.5-30% of co-polymeric amount of substance to be foamed, then by band
There is the copolymerized polymer melt to be foamed of water and foaming agent to be foamed in extrusion foaming machine die orifice or injection foaming machine mold cavity
Shaping, obtains copolymerized polymer foam；
The foaming agent is physical blowing agent or CBA；
If copolymerized polymer to be foamed is module shape and is free of CBA, copolymerized polymer to be foamed is put into moulded from foam
In mould, and water is added, copolymerized polymer to be foamed is completely submerged in water, physical blowing agent is added into mould, heated,
Pressurization is kept, in equilibrium process, foaming agent and water are immersed in copolymerized polymer module to be foamed, are obtained containing the pending of water
Copolymerized polymer module is steeped, die sinking foaming, obtains copolymerized polymer foam；
If copolymerized polymer to be foamed is module shape and contains CBA, copolymerized polymer to be foamed is put into moulded from foam mould
In tool, and water is added, copolymerized polymer to be foamed is completely submerged in water, temperature-pressure, in equilibrium process, water is immersed in
In copolymerized polymer module to be foamed, the copolymerized polymer module to be foamed containing water is obtained, die sinking foaming, obtains co-polymeric
Thing foam.
4. the preparation method of the copolymerized polymer foam with hydrophilic units according to claim 1-3 any one,
Characterized in that, the copolymerized polymer of the hydrophilic structure unit containing 0.2wt%-40wt% is replaced with into composite, it is multiple
Condensation material does not chemically react below blowing temperature, with water, and can use extrusion foaming, moulded from foam, injection foaming
Middle one or more methods prepare foamed material, the copolymerization containing 0.2wt%-40wt% hydrophilic structure units in composite
The content of polymer is no less than 40wt%.
5. the preparation method of the copolymerized polymer foam with hydrophilic units according to claim 1-3 any one,
Characterized in that, the copolymerized polymer containing 0.2wt%-40wt% hydrophilic structure units is polypropylene-polyoxyethylene
The graft polymers of ether, the graft polymers of polyethylene-polyoxyethylene ether, polystyrene-polyoxyethylene ether graft polymers,
The graft polymers of polyvinyl chloride-APEO, the block polymer of polypropylene-APEO, polyethylene-polyoxyethylene
The block polymerization of the block polymer of ether, the block polymer, polyvinyl chloride-APEO of polystyrene-polyoxyethylene ether
It is thing, ethene-vinyl acetate polymer, polyacrylic maleic acid grafted polymers, polyacrylic maleic anhydride grafted polymer, poly-
The maleate graft polymers of propylene, the maleic acid grafted polymers of polyethylene, polyethylene maleic anhydride grafted polymer,
The maleic anhydride grafting of the maleate graft polymers of polyethylene, the maleic acid grafted polymers of polystyrene, polystyrene
Polymer, the maleate graft polymers of polystyrene, the maleic acid grafted polymers of polyvinyl chloride, the Malaysia of polyvinyl chloride
It is Anhydride-grafted polymers, the maleate graft polymers of polyvinyl chloride, polyacrylic acrylic acid graft polymer, polyacrylic
Graft polymerization of acrylic ester thing, the acrylic acid graft polymer of polyethylene, the graft polymerization of acrylic ester thing of polyethylene, polyphenyl second
The acrylic acid graft polymer of alkene, the graft polymerization of acrylic ester thing of polystyrene, polyvinyl chloride acrylic acid graft polymer,
The graft polymerization of acrylic ester thing of polyvinyl chloride, polyacrylic methacrylic acid graft polymers, polyacrylic methacrylic acid
Ester graft polymers, the methacrylic acid graft polymers of polyethylene, methacrylate graft polymers, the polyphenyl of polyethylene
The methacrylic acid graft polymers of ethene, the methacrylate graft polymers of polystyrene, the methyl-prop of polyvinyl chloride
Olefin(e) acid graft polymers, the methacrylate graft polymers of polyvinyl chloride, polyacrylic Itaconic Acid Grafted polymer, poly- third
The itaconate graft polymers of alkene, the Itaconic Acid Grafted polymer of polyethylene, the itaconate graft polymers, poly- of polyethylene
The Itaconic Acid Grafted polymer of styrene, the itaconate graft polymers of polystyrene, the Itaconic Acid Grafted of polyvinyl chloride gather
Compound, the itaconate graft polymers of polyvinyl chloride, polyacrylic fumaric acid graft polymers, polyacrylic fumarate connect
Branch polymer, the fumaric acid graft polymers of polyethylene, the fumarate graft polymers of polyethylene, the fumaric acid of polystyrene
Graft polymers, the fumarate graft polymers of polystyrene, the fumaric acid graft polymers of polyvinyl chloride, polyvinyl chloride
Fumarate graft polymers, polyacrylic starch graft copolymers, the starch graft copolymers of polyethylene, the shallow lake of polystyrene
Powder graft polymers, polyvinyl chloride starch graft copolymers in one or more.
6. the preparation method of the copolymerized polymer foam with hydrophilic units according to claim 1-3 any one,
Characterized in that, in the copolymerized polymer to be foamed, the mass fraction of hydrophilic structure unit is 1wt%-30wt%.
7. the preparation method of the copolymerized polymer foam with hydrophilic units according to claim 1-3 any one,
Characterized in that, the CBA is sodium acid carbonate, ammonium carbonate, N, N- dinitrosopentamethlyene tetramines, N, N- diformazans
Bis- sub- terephthalate amine of base-N, N-, azodicarbonamide, azodiisobutyronitrile, azoformic acid isopropyl ester, azoformic acid two
Ethyl ester, two azoaminobenzenes, Barium azodicarboxylate, 4,4 ,-disulfonyl hydrazide diphenyl ether, to benzene sulfonyl hydrazide, 3,3- disulfonyl hydrazides two
Benzene sulfone, 4,4, the one or more in-two benzene disulfohydrazides, benzen 1,3 disulphonyl hydrazide, 1,4- benzene disulfohydrazides.
8. the preparation method of the copolymerized polymer foam with hydrophilic units according to claim 1-3 any one,
Characterized in that, the physical blowing agent is in carbon dioxide, nitrogen, air, argon gas, methane, ethane, propane, butane, pentane
One or more.
9. the preparation method of the copolymerized polymer foam according to claim 1 with hydrophilic units, it is characterised in that
Step 1 be granulated before or/and step 2 melting mixing during, by bubble nucleating agent, antioxidant, antistatic additive, antiseptic,
One or more in plasticizer, lubricant, brightener, conductive auxiliary agent, crystal controlling agent are added in system.
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