CN103160045B - A kind of polyvinyl-chloride foam material and preparation method thereof - Google Patents
A kind of polyvinyl-chloride foam material and preparation method thereof Download PDFInfo
- Publication number
- CN103160045B CN103160045B CN201110414511.4A CN201110414511A CN103160045B CN 103160045 B CN103160045 B CN 103160045B CN 201110414511 A CN201110414511 A CN 201110414511A CN 103160045 B CN103160045 B CN 103160045B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl
- foam material
- chloride
- pvc
- chloride foam
- 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 kind of polyvinyl-chloride foam material, described polyvinyl-chloride foam material adopts polyvinyl chloride (PVC) RESINS to be main raw material, without the need to adding foam stabilizer, forms crosslinking structure by mixing and molding, electron radiation and foamable; Described polyvinyl-chloride foam material is artificial polyvinyl chloride leather foam material.Correspondingly, the invention also discloses a kind of preparation method of polyvinyl-chloride foam material, after polyvinyl chloride (PVC) RESINS and auxiliary agent mixing and molding, by the pvc material foamable through overshoot, obtain polyvinyl-chloride foam material.Adopt the present invention, described polyvinyl-chloride foam material unit cell rate is high, abscess range of aperture size is narrow, distribution of cells is even, intensity is high, and quality is light, has the material of good elasticity, and complete processing is simple, raw materials cost is low, production efficiency is high, improve controllability and the homogeneity of polyvinyl-chloride foam material foaming.
Description
Technical field
The present invention relates to the Technology field of pvc material, particularly a kind of polyvinyl-chloride foam material and preparation method thereof.
Background technology
In the existing method of cross-linking radiation that utilizes in the technology of producing Foamed polyvinyl chloride material, the mainly chemical process foaming of leatheroid foaming technique, namely adds whipping agent and foams.Whipping agent generally adopts Cellmic C 121, and the sub-methyne tetramine of dinitroso, to methylsulfonamides or Diisopropyl azodicarboxylate.
Below for Cellmic C 121 (hereinafter referred to as AC) whipping agent, polyvinyl chloride (hereinafter referred to as PVC) melt temperature progressively raises, viscosity degradation, and AC decomposes quickening, and air pressure increases; When bubble internal gas pressure is greater than PVC melt tension, bubble will increase; When air pressure equals PVC melt tension, it is constant that bubble will maintain its size, until the sizing of PVC melt cooling.If PVC melt viscosity is too low, and when AC gas forming amount is excessive, crafters can be made to increase and strengthen, when steeping wall and being too thin, PVC melt film tension force is too little, cell collapse easily occurs and occurs collapsing bubble and wearing bubble phenomenon.
Therefore, the dispersiveness suitable stablizer being selected to make it act on AC whipping agent and utilize it in PVC plastic, finds the trim point of get angry air pressure and the PVC melt tension of AC, in leatheroid is produced, especially seem important.Conventional method has: one, fatty acid metal salt, liquid metal one package stabilizer class and partial metal oxide thing, they can reduce the decomposition temperature of AC whipping agent to some extent, and wherein major part also can accelerate decomposition speed.Two, foam stabilizer (ACR) processing aid is added, to improve PVC melt viscosity, ACR auxiliary agent and intermetallic composite coating face clinging power are strong and good with the chemical affinity of polyvinyl chloride resin, and molecular weight ratio PVC's is much bigger, be wound around with the molecular chain of PVC, form a similar reticulated structure, reduce the slippage of polyvinyl chloride resin, shearing is transmitted, thus strengthen mechanical energy be transformed into plasticizing capacity.Play the effect that not only can promote to plastify but also can improve PVC melt viscosity, impel PVC artificial leather foaming layer evenly can form unit cell.
But in reality is produced, although the trim point of get angry air pressure and the PVC melt tension of AC can be solved in order to upper method, these methods all to enterprise's increase cost, so will solve cost height in prior art is industry problem demanding prompt solution.Thus, the leatheroid foam material technology providing a kind of electron irradiation that flexible PVC melt strength is improved is necessary.
Summary of the invention
Embodiment of the present invention technical problem to be solved is, provides a kind of polyvinyl-chloride foam material and preparation method thereof, and described polyvinyl-chloride foam material unit cell rate is high, abscess range of aperture size is narrow, and distribution of cells is even, and intensity is high, quality is light, and has good elasticity; Preparation method's complete processing of described polyvinyl-chloride foam material is simple, raw materials cost is low, production efficiency is high, improves controllability and the homogeneity of polyvinyl-chloride foam material foaming.
For reaching above-mentioned technique effect, embodiments provide a kind of polyvinyl-chloride foam material, described polyvinyl-chloride foam material adopts polyvinyl chloride (PVC) RESINS to be main raw material, without the need to adding foam stabilizer, forms crosslinking structure by mixing and molding, electron radiation and foamable;
Described polyvinyl-chloride foam material is artificial polyvinyl chloride leather foam material.
Preferably, described foam stabilizer is acrylic acid esters co-polymer.
Preferably, described polyvinyl-chloride foam material is as follows in the main raw material formula of mass parts:
Polyvinyl chloride (PVC) RESINS 100 parts
60 ~ 120 parts, softening agent
Whipping agent 4 ~ 10 parts
Stablizer 1 ~ 5 part
Sensitizing agent 0.1 ~ 10 part;
The K value of described polyvinyl chloride (PVC) RESINS is 58 ~ 71, and the polymerization degree is 700 ~ 2500;
Described softening agent is n-butyl phthalate, dinoctyl phthalate, dioctyl phthalate (DOP), the one in dimixo-octyl phthalate and diisooctyl isophthalate or combination;
Described whipping agent is Cellmic C 121, and the sub-methyne tetramine of dinitroso, to the one in methylsulfonamides and Diisopropyl azodicarboxylate or combination;
Described stablizer is calcium stearate, barium stearate, cadmium stearate, Zinic stearas, the one in organotin or combination;
Described sensitizing agent is trimethylolpropane trimethacrylate, Viscoat 295, glycol ether diacrylate, the one in triallyl isocyanate or combination.
Preferably, the temperature of described mixing and molding is 80 ~ 200 DEG C;
The radiation dose of described electron radiation is 10 ~ 1100KGy;
The temperature of described foamable is 180 ~ 260 DEG C.
Preferably, the degree of crosslinking of described polyvinyl-chloride foam material is 0 ~ 90%.
Correspondingly, embodiments provide a kind of preparation method of polyvinyl-chloride foam material, comprising:
By the polyvinyl chloride (PVC) RESINS of 100 parts, 60 ~ 120 parts of softening agent, 4 ~ 10 parts of whipping agents, 1 ~ 5 part
Stablizer and 0.1 ~ 10 part of sensitizing agent mixing and molding under the temperature condition of 80 ~ 200 DEG C, obtain just base;
Be the electron radiation of 10 ~ 1100KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 0 ~ 90%;
By the described pvc material through overshoot foamable under the temperature condition of 180 ~ 260 DEG C, obtain polyvinyl-chloride foam material.
Preferably, the K value of described polyvinyl chloride (PVC) RESINS is 58 ~ 71, and the polymerization degree is 700 ~ 2500;
Described softening agent is n-butyl phthalate, dinoctyl phthalate, dioctyl phthalate (DOP), the one in dimixo-octyl phthalate and diisooctyl isophthalate or combination;
Described whipping agent is Cellmic C 121, and the sub-methyne tetramine of dinitroso, to the one in methylsulfonamides and Diisopropyl azodicarboxylate or combination;
Described stablizer is calcium stearate, barium stearate, cadmium stearate, Zinic stearas, the one in organotin or combination;
Described sensitizing agent is trimethylolpropane trimethacrylate, Viscoat 295, glycol ether diacrylate, the one in triallyl isocyanate or combination.
Preferably, be the electron radiation of 10 ~ 1100KGy by described just base through radiation dose, obtaining degree of crosslinking is in the pvc material step of 0 ~ 90%, comprising:
Being the electron radiation of 10 ~ 24KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 0 ~ 30%;
Being the electron radiation of 24 ~ 36KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 30 ~ 50%;
Being the electron radiation of 36 ~ 1100KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 50 ~ 90%.
Preferably, described polyvinyl-chloride foam material is artificial polyvinyl chloride leather foam material.
Implement the present invention and there is following beneficial effect:
The present invention is about a kind of polyvinyl-chloride foam material, compared with prior art, the present invention first adopts polyvinyl chloride (PVC) RESINS (being called for short PVC below) and auxiliary agent mixing and molding, without the need to adding foam stabilizer, after obtaining first base, be irradiation source again with electron rays, polyvinyl chloride (PVC) RESINS is after electron beam irradiation, and foaming at a certain temperature obtains polyvinyl-chloride foam material.This polyvinyl-chloride foam material unit cell rate is high, and abscess range of aperture size is narrow, and distribution of cells is even, and intensity is high, and quality is light, and has good elasticity.
First, PVC is after electron beam irradiation, under the radiation effect of electron beam, a large amount of living radicals is created between macromolecular chain due to its inside, when two free radical close proximity and the molecular chain at free radical place can free-moving time, just be combined with each other formation cross-link bond, is so just tridimensional network by two-dimensional linear thaumatropy before.At high temperature viscosity is high to have the material of tridimensional network, be enough to opposing and cause occurring perforated phenomenon because gas forming amount increases, namely there is abscess-size with even respectively, the feature that unit cell rate is high, thus foam material is had, and intensity is high, quality light and the advantage of good springiness.
Secondly, PVC utilizes radiation crosslinking foaming technique, and the number by irradiation dose controls the degree of crosslinking of foam material, thus can design the foam material in different abscess aperture, be conducive to producing varying strength and elastic product, improve the controllability of PVC board foaming.
Again, PVC utilizes radiation crosslinking foaming technique, realizes product homogeneous cross-link at the same temperature, and thus foam material is homogeneous, improves the quality of products.
The present invention is also about the preparation method of above-mentioned polyvinyl-chloride foam material, this preparation method utilizes radiation crosslinking foaming technique to prepare polyvinyl-chloride foam material, get angry air pressure and the PVC melt tension of AC whipping agent is made to reach a trim point, and complete processing is simple, production efficiency is high, applied range, energy-conserving and environment-protective, improve controllability and the homogeneity of polyvinyl-chloride foam material foaming.Specifically comprise: 1, nonpoisonous and tasteless by radiation crosslinking foaming technique, reduce atmospheric pollution.2, radiation crosslinking foaming technological process is easy to control, and starting material such as base resin or whipping agent are selected to be more prone to.3, radiation crosslinking technique realizes product to be at the same temperature cross-linked, thus homogeneous, and can control the size of product degree of crosslinking.4, irradiation technique can realize product homogeneous cross-link at arbitrary temperature, and then foams, and therefore expansion rate is fast.5, control the dosage of radiation and dose rate, the various foam materialss that degree of crosslinking difference, pore size are different, expansion ratio differs greatly can be obtained easily.6, this technique does not need to use foam stabilizer, reduces raw materials cost, expands with industrial scale, and output increases, and radiation crosslinking foaming process costs obviously declines.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of a kind of polyvinyl-chloride foam material of the present invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiments provide a kind of polyvinyl-chloride foam material, described polyvinyl-chloride foam material adopts polyvinyl chloride (PVC) RESINS to be main raw material, without the need to adding foam stabilizer, forms crosslinking structure by mixing and molding, electron radiation and foamable;
Described polyvinyl-chloride foam material is artificial polyvinyl chloride leather foam material.
Described foam stabilizer is acrylic acid esters co-polymer.
Foam stabilizer belongs to the intermiscibility that tensio-active agent can increase each component, plays a part emulsification foam material, stable foam and adjustment abscess.But it is high that the present invention can obtain unit cell rate without the need to foam stabilizer, and abscess range of aperture size is narrow, distribution of cells is even, and intensity is high, and quality is light, and has the foam material of favorable elasticity.This is that to prepare PVC artificial leather foam material due to radiation crosslinking be after electron beam irradiation, under the effect of high-power electron beam, a large amount of living radicals is created between macromolecular chain due to its inside, when two free radical close proximity and the molecular chain at free radical place can free-moving time, just be combined with each other formation cross-link bond, be so just tridimensional network by two-dimensional linear thaumatropy before, thus significantly improve the melt strength of PVC.In addition, without the need to adding foam stabilizer during owing to producing, reduce raw materials cost, along with industrial scale increases, output increases, and uses the production cost of electron radiation cross-linking method obviously to decline.
Polyvinyl-chloride foam material of the present invention is as follows in the main raw material formula of mass parts:
Polyvinyl chloride (PVC) RESINS 100 parts
60 ~ 120 parts, softening agent
Whipping agent 4 ~ 10 parts
Stablizer 1 ~ 5 part
Sensitizing agent 0.1 ~ 10 part;
The K value of described polyvinyl chloride (PVC) RESINS is 58 ~ 71, and the polymerization degree is 700 ~ 2500;
Preferably, described polyvinyl-chloride foam material is as follows in the main raw material formula of mass parts:
Polyvinyl chloride (PVC) RESINS 100 parts
70 ~ 100 parts, softening agent
Whipping agent 5 ~ 8 parts
Stablizer 2 ~ 4 parts
Sensitizing agent 0.1 ~ 5 part;
The K value of described polyvinyl chloride (PVC) RESINS is 58 ~ 71, and the polymerization degree is 700 ~ 2500;
Described softening agent is n-butyl phthalate, dinoctyl phthalate, dioctyl phthalate (DOP), the one in dimixo-octyl phthalate and diisooctyl isophthalate or combination;
Described whipping agent is Cellmic C 121, and the sub-methyne tetramine of dinitroso, to the one in methylsulfonamides and Diisopropyl azodicarboxylate or combination;
Described stablizer is calcium stearate, barium stearate, cadmium stearate, Zinic stearas, the one in organotin or combination;
Described sensitizing agent is trimethylolpropane trimethacrylate, Viscoat 295, glycol ether diacrylate, the one in triallyl isocyanate or combination.
It should be noted that, radiation dose, plasticising dosage and sensitization dosage all can according to the intensity of polyvinyl-chloride foam material needed for client, soft durometer, and abscess-size carries out regulating.
It is a progressive decomposition course that stablizer decomposes AC whipping agent.Its foaming varies with temperature and changes, even if after PVC goes out baking oven, its foaming can not be stopped at once, whipping agent decomposes still can maintain for some time, thus cause blowing temperature not easily to grasp,, there is the cold spot of pin hole, even perforated phenomenon in the artificial leather product surface of a little accidentally producing and rough and uneven in surface.Because foam material is after electron radiation, its melt strength increases, viscosity increases, thus avoid because PVC melt viscosity is too low, and AC whipping agent gas forming amount excessive time, crafters increases increasing, and when steeping wall and being too thin, PVC melt film tension force is too little, cell collapse easily occurs and occurs collapsing bubble and wearing bubble phenomenon.
The temperature of described mixing and molding is 80 ~ 200 DEG C;
Preferably, the temperature of described mixing and molding is 100 ~ 180 DEG C.
The radiation dose of described electron radiation is 10 ~ 1100KGy;
Preferably, the radiation dose of described electron radiation is 15 ~ 300KGy.
Further preferably, the radiation dose of described electron radiation is 15 ~ 150KGy.
The temperature of described foamable is 180 ~ 260 DEG C.
Preferably, the temperature of described foamable is 200 ~ 240 DEG C.
It should be noted that, in process that is mixing and base at the beginning of being shaped to, melting temperature setting range should higher than AC foaming agent decomposition temperature, and wherein the present invention uses the decomposition temperature of AC whipping agent to be 200 ~ 240 DEG C, therefore, mixing temperature must not more than the lower limit 200 DEG C of AC foaming agent decomposition temperature.
The degree of crosslinking of described polyvinyl-chloride foam material is 0 ~ 90%.
Preferably, the degree of crosslinking of described polyvinyl-chloride foam material is 10 ~ 65%.
As shown in Figure 1, embodiments provide a kind of preparation method of polyvinyl-chloride foam material, comprising:
S101, by the polyvinyl chloride (PVC) RESINS of 100 parts, 60 ~ 120 parts of softening agent, 4 ~ 10 parts of whipping agents, 1 ~ 5 part of sensitizing agent and 0.1 ~ 10 part of stablizer mixing and molding under the temperature condition of 80 ~ 200 DEG C, obtains just base;
In step S101, comprising:
The polyvinyl chloride (PVC) RESINS of 100 parts, 60 ~ 120 parts of softening agent, 4 ~ 10 parts of whipping agents, 1 ~ 5 part of sensitizing agent and 0.1 ~ 10 part of stablizer are joined mixing roll, and control temperature carries out mixing at 80 ~ 200 DEG C, until each component reaches dispersed;
By the material cooling forming after mixing, obtain just base;
The K value of polyvinyl chloride (PVC) RESINS is 58 ~ 71, and the polymerization degree is 700 ~ 2500;
Described softening agent is n-butyl phthalate, dinoctyl phthalate, dioctyl phthalate (DOP), the one in dimixo-octyl phthalate and diisooctyl isophthalate or combination;
Described whipping agent is Cellmic C 121, and the sub-methyne tetramine of dinitroso, to the one in methylsulfonamides and Diisopropyl azodicarboxylate or combination;
Described stablizer is calcium stearate, barium stearate, cadmium stearate, Zinic stearas, the one in organotin or combination;
Described sensitizing agent is trimethylolpropane trimethacrylate, Viscoat 295, glycol ether diacrylate, the one in triallyl isocyanate or combination.
It should be noted that, radiation dose, plasticising dosage and sensitization dosage all can according to the intensity of polyvinyl-chloride foam material needed for client, soft durometer, and abscess-size carries out regulating.
S102, is the electron radiation of 10 ~ 1100KGy by described just base through radiation dose, obtains the pvc material that degree of crosslinking is 0 ~ 90%.
In step s 102, comprising:
By mixing through rumbatron, be after the electron rays radiation of 20 ~ 320KV by radiation voltage, obtain the pvc material that degree of crosslinking is 0 ~ 90%;
The radiation dose of described electron rays is 10 ~ 1100KGy.
Preferably, the radiation voltage of rumbatron is 30 ~ 250KV, and the radiation dose of electron radiation is 15 ~ 300KGy.
Further preferably, the radiation dose of electron radiation is 15 ~ 150KGy.
The impact of different radiation dose on the degree of crosslinking of product is: along with the increase of radiation dose, degree of crosslinking is larger, as shown in table 1.
The different radiation dose of table 1 is to the contrast of the degree of crosslinking of product
| Sequence number | 1 | 2 | 3 |
| Irradiation dose/KGy | 15～24 | 24～36 | 36～1000 |
| Degree of crosslinking/% | 0～30 | 30～50 | 50～90 |
No. 1, No. 2 and No. 3 sample material formulas are all:
Polyvinyl chloride (PVC) RESINS 100 parts
70 ~ 100 parts, softening agent
Whipping agent 5 ~ 8 parts
Stablizer 2 ~ 4 parts
Sensitizing agent 0.1 ~ 3 part;
As shown in Table 1, due to 3 kinds of samples composition of raw materials with the mixing forming process conditions of process all identical, but the radiation dose when using electron radiation increases successively, the energy provided along with electron beam increases, produce more free radical, be conducive to carrying out the reaction that Radical rearrangement etc. is convenient to be cross-linked, thus improve the degree of crosslinking of product.
S103, by the described pvc material through overshoot foamable under the temperature condition of 180 ~ 260 DEG C, obtains polyvinyl-chloride foam material.
In step s 103, comprising:
Under temperature being increased to the temperature condition of 180 ~ 260 DEG C, blowing agent AC decomposes generation gas;
Therefore the described pvc material through overshoot forms adjoining dimensions, and the abscess be evenly distributed, obtains polyvinyl-chloride foam material.
It should be noted that, metal ion at a certain temperature in PVC material obtains enough energy, collide with the some molecules on blowing-agent particle, make it activate and decompose generation gas, if at this moment PVC material does not form homogeneous phase melt, gas will be escaped and be evaporate in air from the space of PVC material, if PVC material forms homogeneous phase melt, so gas will be enclosed near AC particle surface and form nuclei of bubbles, and PVC at this moment can be made to expect, and foaming depends primarily on the coupling of PVC melt viscosity and whipping agent gas forming amount.
With regard to the gas forming amount of whipping agent and the relation of melt viscosity, when PVC melt viscosity is excessive, although AC constantly decomposes in nuclei of bubbles, air pressure constantly increases, but because gas tension in nuclei of bubbles is less than PVC melt tension, bubble is just not easily grown up, thus causes artificial leather product expansion ratio low, and foaming effect is bad.As PVC melt temperature progressively raises, viscosity degradation, AC decomposes quickening, and air pressure increases; When bubble internal gas pressure is greater than PVC melt tension, bubble will increase; When air pressure equals PVC melt tension, it is constant that bubble will maintain its size, until the sizing of PVC melt cooling.If PVC melt viscosity is too low, and when AC gas forming amount is excessive, crafters can be made to increase and strengthen, when steeping wall and being too thin, PVC melt film tension force is too little, cell collapse easily occurs and occurs collapsing bubble and wearing bubble phenomenon.
After crosslinked by electron radiation, at high temperature viscosity is high to have the material of tridimensional network, be enough to opposing and cause occurring perforated phenomenon because gas forming amount increases, namely there is abscess-size and be evenly distributed, the feature that unit cell rate is high, thus foam material is had, and intensity is high, quality light and the advantage of good springiness.
To chemically crosslinked gained polyvinyl-chloride foam material in the polyvinyl-chloride foam material of crosslinking electron beam irradiation gained of the present invention and prior art, be adopted to compare below, specific as follows:
Embodiment, with the polyvinyl-chloride foam material of above-mentioned preparation method's crosslinking electron beam irradiation gained; Reference example, adopt chemically crosslinked gained polyvinyl-chloride foam material, two kinds of different methods gained polyvinyl-chloride foam materials are as shown in table 2.
As shown in Table 2, embodiment does not use foam stabilizer, have adjusted the deal of sensitizing agent and stablizer simultaneously, the abscess that the foam material obtained basically forms is that single bubble and range of cell sizes are narrow, distribution of cells is even, occurs that abscess merges relative to the foam material of chemically crosslinked gained, and the situation that size is uneven, not only improve the outward appearance of foam material, also therefore improve intensity and the elasticity of foam material simultaneously.
By two products produced of filling a prescription, find after contrast, by such formulating of recipe, after PVC can be made to carry out irradiation, degree of crosslinking is even, and during foaming, distribution of cells is even.The present invention makes PVC self form crosslinking structure with irradiation method, without the need to introducing the network structure of other polymeric system, more not needing to add foam stabilizer (ACR) auxiliary agent, thus reducing material cost, simplifying production technique, enhance productivity.Pass through electron beam irradiation, its uniform irradiation can be ensured and reach the degree of crosslinking index of regulation, thus foam bubble is more evenly distributed, also can realize higher rate of closed hole simultaneously, and design abscess aperture by controlling degree of crosslinking, raising controllability, final production flexible PVC leatheroid foamed products is out higher than the intensity of general AC foaming PVC artificial leather material, quality is lighter, has the stronger market competitiveness from price.
The present invention is further illustrated below with specific embodiment.
Embodiment 1
With the polyvinyl chloride (PVC) RESINS of 100 parts of polymerization degree 700 ~ 2500,65 parts of plasticizer phthalic acid di-n-butyls, 4 parts of whipping agent Cellmic C 121s, 1.2 parts of stablizer calcium stearates, 0.1 part of sensitizing agent trimethylolpropane trimethacrylate is raw material, mixing and molding under the temperature condition of 80 ~ 200 DEG C, obtains just base.And then by mixing obtain first base through rumbatron, adopt radiation dose to be after the electron rays radiation of 20KGy, obtain the polyvinyl-chloride foam material that degree of crosslinking is 10%.By the described pvc material through overshoot foamable under the temperature condition of 180 DEG C, obtain polyvinyl-chloride foam material.
Embodiment 2
With the polyvinyl chloride (PVC) RESINS of 100 parts of polymerization degree 700 ~ 2500,88 parts of plasticizer phthalic acid di-n-octyls, 5.5 parts of sub-methyne tetramines of whipping agent dinitroso, 2.3 parts of stablizer barium stearates, 3.1 parts of sensitizing agent Viscoat 295s are raw material, mixing and molding under the temperature condition of 80 ~ 200 DEG C, obtains just base.And then by mixing obtain first base through rumbatron, adopt radiation dose to be after the electron rays radiation of 26KGy, obtain the polyvinyl-chloride foam material that degree of crosslinking is 35%.By the described pvc material through overshoot foamable under the temperature condition of 200 DEG C, obtain polyvinyl-chloride foam material.
Embodiment 3
With the polyvinyl chloride (PVC) RESINS of 100 parts of polymerization degree 700 ~ 2500,110 parts of softening agent diisooctyl isophthalates, 9.2 parts of whipping agents are to methylsulfonamides, 4.8 parts of stablizer cadmium stearates, 8.9 parts of sensitizing agent glycol ether diacrylates are raw material, mixing and molding under the temperature condition of 80 ~ 200 DEG C, obtains just base.And then by mixing obtain first base through rumbatron, adopt radiation dose to be after the electron rays radiation of 900KGy, obtain the polyvinyl-chloride foam material that degree of crosslinking is 82%.By the described pvc material through overshoot foamable under the temperature condition of 240 DEG C, obtain polyvinyl-chloride foam material.
Embodiment 4
With the polyvinyl chloride (PVC) RESINS of 100 parts of polymerization degree 700 ~ 2500,95 parts of dimixo-octyl phthalates, 7.3 parts of whipping agent Diisopropyl azodicarboxylates, 3.5 parts of stablizer Zinic stearass, 4.2 parts of sensitizing agent triallyl isocyanates are raw material, mixing and molding under the temperature condition of 80 ~ 200 DEG C, obtain just base.And then by mixing obtain first base through rumbatron, adopt radiation dose to be after the electron rays radiation of 36KGy, obtain the polyvinyl-chloride foam material that degree of crosslinking is 50%.By the described pvc material through overshoot foamable under the temperature condition of 260 DEG C, obtain polyvinyl-chloride foam material.
In sum, implement the present invention and there is following beneficial effect:
The present invention is about a kind of polyvinyl-chloride foam material, compared with prior art, the present invention first adopts polyvinyl chloride (PVC) RESINS (being called for short PVC below) and auxiliary agent mixing and molding, without the need to adding foam stabilizer, after obtaining first base, be irradiation source again with electron rays, polyvinyl chloride (PVC) RESINS is after electron beam irradiation, and foaming at a certain temperature obtains polyvinyl-chloride foam material.This polyvinyl-chloride foam material unit cell rate is high, and abscess range of aperture size is narrow, and distribution of cells is even, and intensity is high, and quality is light, and has good elasticity.
First, PVC is after electron beam irradiation, under the radiation effect of electron beam, a large amount of living radicals is created between macromolecular chain due to its inside, when two free radical close proximity and the molecular chain at free radical place can free-moving time, just be combined with each other formation cross-link bond, is so just tridimensional network by two-dimensional linear thaumatropy before.At high temperature viscosity is high to have the material of tridimensional network, be enough to opposing and cause occurring perforated phenomenon because gas forming amount increases, namely there is abscess-size with even respectively, the feature that unit cell rate is high, thus foam material is had, and intensity is high, quality light and the advantage of good springiness.
Secondly, PVC utilizes radiation crosslinking foaming technique, and the number by irradiation dose controls the degree of crosslinking of foam material, thus can design the foam material in different abscess aperture, be conducive to producing varying strength and elastic product, improve the controllability of PVC board foaming.
Again, PVC utilizes radiation crosslinking foaming technique, realizes product homogeneous cross-link at the same temperature, and thus foam material is homogeneous, improves the quality of products.
The present invention is also about the preparation method of above-mentioned polyvinyl-chloride foam material, this preparation method utilizes radiation crosslinking foaming technique to prepare polyvinyl-chloride foam material, get angry air pressure and the PVC melt tension of AC whipping agent is made to reach a trim point, and complete processing is simple, production efficiency is high, applied range, energy-conserving and environment-protective, improve controllability and the homogeneity of polyvinyl-chloride foam material foaming.Specifically comprise: 1, nonpoisonous and tasteless by radiation crosslinking foaming technique, reduce atmospheric pollution.2, radiation crosslinking foaming technological process is easy to control, and starting material such as base resin or whipping agent are selected to be more prone to.3, radiation crosslinking technique realizes product to be at the same temperature cross-linked, thus homogeneous, and can control the size of product degree of crosslinking.4, irradiation technique can realize product homogeneous cross-link at arbitrary temperature, and then foams, and therefore expansion rate is fast.5, control the dosage of radiation and dose rate, the various foam materialss that degree of crosslinking difference, pore size are different, expansion ratio differs greatly can be obtained easily.6, this technique does not need to use foam stabilizer, reduces raw materials cost, expands with industrial scale, and output increases, and radiation crosslinking foaming process costs obviously declines.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (7)
1. a polyvinyl-chloride foam material, is characterized in that, described polyvinyl-chloride foam material adopts polyvinyl chloride (PVC) RESINS to be main raw material, without the need to adding foam stabilizer, forms crosslinking structure by mixing and molding, electron radiation and foamable;
Described polyvinyl-chloride foam material is artificial polyvinyl chloride leather foam material;
Wherein, described polyvinyl-chloride foam material is as follows in the main raw material formula of mass parts:
Polyvinyl chloride (PVC) RESINS 100 parts
70 ~ 100 parts, softening agent
Whipping agent 5 ~ 8 parts
Stablizer 2 ~ 4 parts
Sensitizing agent 0.1 ~ 5 part;
The K value of described polyvinyl chloride (PVC) RESINS is 58 ~ 71, and the polymerization degree is 700 ~ 2500;
The temperature of described mixing and molding is 100 ~ 180 DEG C;
The radiation dose of described electron radiation is 15 ~ 150KGy;
The temperature of described foamable is 200 ~ 240 DEG C
The degree of crosslinking of described polyvinyl-chloride foam material is 10 ~ 65%.
2. polyvinyl-chloride foam material as claimed in claim 1, it is characterized in that, described foam stabilizer is acrylic acid esters co-polymer.
3. polyvinyl-chloride foam material as claimed in claim 1, it is characterized in that, described softening agent is n-butyl phthalate, dinoctyl phthalate, dioctyl phthalate (DOP), the one in dimixo-octyl phthalate and diisooctyl isophthalate or combination;
Described whipping agent is Cellmic C 121, and the sub-methyne tetramine of dinitroso, to the one in methylsulfonamides and Diisopropyl azodicarboxylate or combination;
Described stablizer is calcium stearate, barium stearate, cadmium stearate, Zinic stearas, the one in organotin or combination;
Described sensitizing agent is trimethylolpropane trimethacrylate, Viscoat 295, glycol ether diacrylate, the one in triallyl isocyanate or combination.
4. a preparation method for polyvinyl-chloride foam material, is characterized in that, comprising:
By the polyvinyl chloride (PVC) RESINS of 100 parts, 70 ~ 100 parts of softening agent, 5 ~ 8 parts of whipping agents, 2 ~ 4 parts
Stablizer and 0.1 ~ 5 part of sensitizing agent mixing and molding under the temperature condition of 100 ~ 180 DEG C, obtain just base;
Be the electron radiation of 15 ~ 150KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 10 ~ 65%;
By the described pvc material through overshoot foamable under the temperature condition of 200 ~ 240 DEG C, obtain polyvinyl-chloride foam material;
Wherein, the K value of described polyvinyl chloride (PVC) RESINS is 58 ~ 71, and the polymerization degree is 700 ~ 2500.
5. the preparation method of polyvinyl-chloride foam material as claimed in claim 4, is characterized in that,
Described softening agent is n-butyl phthalate, dinoctyl phthalate, dioctyl phthalate (DOP), the one in dimixo-octyl phthalate and diisooctyl isophthalate or combination;
Described whipping agent is Cellmic C 121, and the sub-methyne tetramine of dinitroso, to the one in methylsulfonamides and Diisopropyl azodicarboxylate or combination;
Described stablizer is calcium stearate, barium stearate, cadmium stearate, Zinic stearas, the one in organotin or combination;
Described sensitizing agent is trimethylolpropane trimethacrylate, Viscoat 295, glycol ether diacrylate, the one in triallyl isocyanate or combination.
6. the preparation method of polyvinyl-chloride foam material as claimed in claim 5, is characterized in that, be the electron radiation of 10 ~ 1100KGy by described just base through radiation dose, obtaining degree of crosslinking is in the pvc material step of 0 ~ 90%, comprising:
Being the electron radiation of 10 ~ 24KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 0 ~ 30%;
Being the electron radiation of 24 ~ 36KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 30 ~ 50%;
Being the electron radiation of 36 ~ 1100KGy by described just base through radiation dose, obtain the pvc material that degree of crosslinking is 50 ~ 90%.
7. the preparation method of the polyvinyl-chloride foam material as described in any one of claim 4 ~ 6, is characterized in that, described polyvinyl-chloride foam material is artificial polyvinyl chloride leather foam material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110414511.4A CN103160045B (en) | 2011-12-13 | 2011-12-13 | A kind of polyvinyl-chloride foam material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110414511.4A CN103160045B (en) | 2011-12-13 | 2011-12-13 | A kind of polyvinyl-chloride foam material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103160045A CN103160045A (en) | 2013-06-19 |
| CN103160045B true CN103160045B (en) | 2015-12-02 |
Family
ID=48583600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110414511.4A Active CN103160045B (en) | 2011-12-13 | 2011-12-13 | A kind of polyvinyl-chloride foam material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103160045B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104775305B (en) * | 2014-01-10 | 2017-03-08 | 安踏（中国）有限公司 | A kind of front water repellent, reverse side nestling-to-skin proof textile and its production method |
| JP6572307B2 (en) * | 2016-03-31 | 2019-09-04 | 積水化学工業株式会社 | Cross-linked polyolefin resin foam sheet and method for producing the same |
| CN106364110A (en) * | 2016-08-30 | 2017-02-01 | 楼钦 | Wear-resistant coat on polyvinyl chloride (PVC) foaming coiled material |
| CN106543584A (en) * | 2016-10-31 | 2017-03-29 | 江苏昊晟塑业科技有限公司 | Automotive trim panel is heat-resisting to use expanded material |
| CN106638013B (en) * | 2016-11-29 | 2019-11-22 | 安徽天安新材料有限公司 | The preparation method of artificial leather and artificial leather |
| CN106827371A (en) * | 2017-01-21 | 2017-06-13 | 温岭东方红车料有限公司 | The processing method of saddle and its set skin |
| CN110724297B (en) * | 2018-07-17 | 2022-03-18 | 泉硕科技股份有限公司 | Foaming master batch for in-mold foaming and manufacturing method thereof |
| CN110426308B (en) * | 2019-06-13 | 2022-06-28 | 加通汽车内饰(常熟)有限公司 | Manufacturing process of EPDM synthetic leather and detection method of crosslinking degree thereof |
| CN112194858A (en) * | 2020-09-29 | 2021-01-08 | 泗县金皖泵业有限公司 | Electron radiation crosslinking elastomer foam for water pump sealing and preparation method thereof |
| CN113321881B (en) * | 2021-06-15 | 2022-09-02 | 东营瑞致新材料有限公司 | PVC foam used as offshore buoyancy material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824194A (en) * | 2010-05-13 | 2010-09-08 | 佛山塑料集团股份有限公司 | Radiated crosslinking PVC (Polyvinyl Chloride) rigid foaming material |
| CN101857705A (en) * | 2010-06-23 | 2010-10-13 | 深圳市帝源电子有限公司 | Nontoxic, anti-heat shrinkable polyvinyl chloride material and manufacturing technology thereof |
-
2011
- 2011-12-13 CN CN201110414511.4A patent/CN103160045B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824194A (en) * | 2010-05-13 | 2010-09-08 | 佛山塑料集团股份有限公司 | Radiated crosslinking PVC (Polyvinyl Chloride) rigid foaming material |
| CN101857705A (en) * | 2010-06-23 | 2010-10-13 | 深圳市帝源电子有限公司 | Nontoxic, anti-heat shrinkable polyvinyl chloride material and manufacturing technology thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103160045A (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103160045B (en) | A kind of polyvinyl-chloride foam material and preparation method thereof | |
| CN107599296B (en) | Micropore injection moulding foaming preparation polylactic acid-natural rubber porous material method and material | |
| CN101824194B (en) | Radiated crosslinking PVC (Polyvinyl Chloride) rigid foaming material | |
| CN104877236A (en) | Radiation crosslinked polypropylene foamed plastic and continuous production method thereof | |
| CN106084303B (en) | A kind of Biodegradable high-molecular is composite porous and preparation method thereof | |
| CN107266765A (en) | A kind of inorganic foamed IXPE foams and preparation method thereof | |
| CN110343286B (en) | Poly (butylene succinate) ionomer foam and preparation method and application thereof | |
| CN108034199A (en) | High filled biodegradable radiation cross-linked foam material and preparation method thereof | |
| CN110982189B (en) | PVC structural foam and preparation method thereof | |
| CN114085455B (en) | Low-density flame-retardant polypropylene foam material and preparation method thereof | |
| CN109651695A (en) | A kind of easy clinkering, high temperature tolerance polyethylene foamed bead and preparation method thereof | |
| CN114106396A (en) | Preparation method of thermoplastic polyurethane foam material | |
| WO2009119325A1 (en) | Aliphatic polyester resin foam, flower arrangement holder made of the foam, and processes for production of both | |
| CN107541031A (en) | A kind of modified PGA or PLGA fully biodegradable foamed material and preparation method thereof | |
| CN108795020A (en) | A kind of graphene-polyurathamc composite material and preparation method | |
| CN111793333A (en) | Preparation method of PET foam core material for wind power blade | |
| CN102888015A (en) | Composite foaming agent and polypropylene foam material prepared from same | |
| CN106832181A (en) | A kind of polyurethane foam material and preparation method thereof | |
| CN116731492A (en) | Hard conductive foam and preparation process thereof | |
| CN107189189B (en) | High-gloss barium and talcum powder blended modified EVA (ethylene-vinyl acetate) foaming material and preparation thereof | |
| CN108858953A (en) | A kind of radio frequency foaming method of EVA material | |
| CN113583465A (en) | High-ductility sponge material and preparation process thereof | |
| CN107325455A (en) | A kind of preparation method of low smell plastic master batch | |
| CN107057183A (en) | Composition, inner container of icebox and preparation method thereof, refrigerator | |
| CN102964720A (en) | Crosslinked PVC (Poly Vinyl Chloride) structure foamed material 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 | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20130619 Assignee: Guangdong Yaoda Financial Leasing Co., Ltd Assignor: GUANGDONG TIANAN NEW MATERIAL Co.,Ltd. Contract record no.: X2020980005499 Denomination of invention: A PVC foaming material and its preparation method Granted publication date: 20151202 License type: Exclusive License Record date: 20200828 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A PVC foaming material and its preparation method Effective date of registration: 20200904 Granted publication date: 20151202 Pledgee: Guangdong Yaoda Financial Leasing Co., Ltd Pledgor: GUANGDONG TIANAN NEW MATERIAL Co.,Ltd. Registration number: Y2020980005712 |