CN101824217B - Polyurethane rubber composition and preparation process thereof - Google Patents

Abstract

The invention provides a high-water-absorptivity degradable polyurethane rubber composition and a preparation method thereof, so that the rubber composition has high water-absorptivity and degradability. The polyurethane rubber composition comprises the following components in parts by weight based on 100 parts by weight of polyester and/or polyether mixed polyurethane rubber: 100 parts of polyester and/or polyether mixed polyurethane rubber; 10-60 parts of a mixture of starch, persulfate and water; 15-60 parts of starch-based super absorbent resin; and other auxiliary agents. The polyurethane rubber composition disclosed by the invention can be chemically degraded and biologically degraded, has high water absorption rate, can adjust the degradation period by different proportions of polyurethane rubbers of different types and/or proportions of chemical degradation products and/or biological degradation products, has the degradation period of 8-42 months, and has the expansion ratio of 300-800% in distilled water.

Description

A kind of polyurethane rubber composition and its preparation process

technical field

The invention relates to a degradable polyurethane rubber composition with excellent biodegradability and chemical degradation ability, and a preparation process of the rubber composition.

Background technique

With the development of the times, the global rubber industry has undergone tremendous changes. The cross-linked rubber produced by the traditional rubber vulcanization process is not easy to degrade after losing its usability, and brings a lot of garbage to the human living environment. Therefore, everyone hopes to use a A cross-linked rubber material that degrades after losing its usability. CN1563155A discloses a water-swellable rubber prepared from a water-swellable resin and a preparation method thereof. Among them, the water-swellable resin is polymerized by polymerizing monomers containing polyoxyethylene ether (meth)acrylate, catalysts, initiators and crosslinking agents in proportion; the water-swellable rubber is composed of water-swellable resins, neoprene, and fillers. , softener, accelerator and anti-aging agent are produced by mixing and vulcanizing. The water-swellable rubber has excellent performance, good ion resistance, and no precipitates after contact with water. The parts by weight are: 50-100 parts of water-swellable resin, 100 parts of neoprene, 20-35 parts of filler, 10-20 parts of softener, 0.5-1.0 parts of accelerator, and 0.5 parts of anti-aging agent. ~1.0 servings. The water-swellable rubber vulcanization composition disclosed in this document mainly uses neoprene, and the water-swellable rubber vulcanization composition is not degradable.

Contents of the invention

The object of the present invention is to provide a highly water-absorbing and degradable polyurethane rubber composition and a preparation method thereof, so that the rubber composition has high water-absorbing property and degradability simultaneously.

A polyurethane rubber composition, based on 100 parts by weight of polyester type and/or polyether type mixed polyurethane rubber, comprises the following components:

Polyester type and/or polyether type mixed polyurethane rubber, 100 parts;

A mixture of starch, persulfate and water, denoted as H, 10-60 parts, wherein the proportion (parts by weight) of starch, persulfate and water is 100: (2-20): (10-35);

Sulfite, 0.5-5 parts;

Stearic acid, 0.5-3 parts;

Zinc oxide, 3-15 parts;

Rubber anti-aging agent, 0-5 parts;

Filling agent, 5-70 parts;

Ester plasticizer, 5-50 parts;

Epoxy resin, 1-30 parts;

Starch-based superabsorbent resin, 15-60 parts;

Foaming agent, 1-20 parts;

Rubber crosslinking agent, 3-15 parts.

Polyurethane rubber of the present invention is a commercially available product, polyester type polyurethane rubber such as AU28 (Millathane28), polyester type HA-1, S type glue, Eelastothane 640 etc.; Polyether type polyurethane rubber such as EU26 (Millathane26), wherein When polyester type and polyether type polyurethane rubber are used together, the ratio of the two can be adjusted arbitrarily.

The starch used may be one or more of bean starch, wheat starch, rice starch, cereal starch or potato starch.

The used persulfate of the present invention can be the alkali metal salt of persulfuric acid such as potassium persulfate, sodium persulfate etc., or the alkaline earth metal salt of persulfuric acid such as calcium persulfate etc., also can be the nonmetallic salt of persulfuric acid such as persulfuric acid Ammonium etc.

Sulfite is soluble in water. The cations contained in sulfite can be non-oxidizing metal ions or non-oxidizing non-metal ions (groups). Metal ions such as sodium ions, potassium ions, etc., non-metal ions such as Ammonium ion, etc.

The rubber antioxidant of the present invention may be one or more of amine antioxidants, phenolic (derivative) antioxidants or benzimidazole antioxidants.

The amine anti-aging agent is selected from N, N'-bis(2-octyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-bis( 1,4-dimethylpentyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine organic complex, etc.

The phenolic (derivative) antioxidant is selected from 3-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 2,2'-thiobis(4-methyl -6-tert-butylphenol) and so on.

The benzimidazole antioxidants include 2-mercaptobenzimidazole and the like.

The filler can be phosphorus-containing inorganic substances selected from ammonium phosphate, calcium superphosphate, tricalcium phosphate, double superphosphate, etc., or other inorganic fillers can be selected from white carbon black, talcum powder, calcium carbonate, magnesium oxide wait.

The ester plasticizer described in the present invention may be one or more of phthalates, aliphatic dibasic acid esters, phosphoric acid esters, fatty acid esters or polyol esters.

The epoxy resin of the present invention is bisphenol A type epoxy resin such as E-44, E-42 etc. which is liquid at normal temperature, or a mixture of the above epoxy resins.

The starch-based superabsorbent resin of the present invention may be a starch-grafted acrylonitrile resin or a starch-grafted acrylic resin.

The foaming agent of the present invention can be an inorganic foaming agent for opening cells such as water, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, potassium borohydride, etc., or an organic foaming agent for opening cells such as Azobisisobutyronitrile, N,N'-dinitrosopentamethylenetetramine, etc., or a mixture of the above inorganic and organic cell opening foaming agents.

The rubber crosslinking agent of the present invention is made up of main crosslinking agent and auxiliary crosslinking agent, and the proportioning (by weight) of main crosslinking agent and auxiliary crosslinking agent is: (3～10): (0.1 ~5). The main cross-linking agent can be organic peroxides, such as one of dicumyl peroxide, dibenzoyl peroxide, etc. At this time, the auxiliary cross-linking agent can be sulfur, sulfur-containing donor compounds such as Qiulan One or more of peroxides, sulfur-containing morpholine derivatives, and triallyl isocyanurate; the main crosslinking agent can also be one of sulfur or sulfur-containing sulfur donor compounds, which The auxiliary crosslinking agent can be one or more of thiazoles, thiurams or sulfenamides.

Rubber composition of the present invention is prepared by the following method:

(1) First prepare a mixture of starch, persulfate and water, and stir at high speed for 5 to 30 minutes to mix the starch, persulfate and water evenly to form a mixture H.

(2) After the polyurethane rubber is masticated in an open mixer or internal mixer for 1 to 5 minutes, add the pre-prepared mixture H to the open mixer or internal mixer, and after mixing for 1 to 5 minutes, add sub Sulphate, react in an open mill or internal mixer for 4 to 10 minutes, so that the starch is partially grafted on the polyurethane molecule, then add stearic acid and zinc oxide, mix for 1 to 5 minutes, then add rubber antioxidant, After kneading for 1 to 3 minutes, add filler, after kneading for 2 to 5 minutes, then add ester plasticizer and epoxy resin, after kneading for 2 to 8 minutes, then add starch-based superabsorbent resin and foam Foaming agent, after mixing for 1 to 5 minutes, add rubber crosslinking agent, after mixing for 2 to 6 minutes, press on the open mill.

(3) After parking at room temperature for 12-24 hours, vulcanize at 130-180°C before use.

The persulfate and sulfite added in the present invention form the initiation system of starch-grafted polyurethane rubber. Under the action of the initiation system, the starch reacts with the mixing type polyurethane, so that the starch is partially grafted on the polyurethane molecules to form a compatibilizer. The interface can increase the compatibility of the starch-based superabsorbent resin and the rubber mixture system, and the remaining ungrafted starch can be used as the biodegradation point of the degradable system.

The added stearic acid and zinc oxide are used as vulcanization activators to form a vulcanization system together with the crosslinking agent and co-crosslinking agent, and the action of the polyurethane rubber can make the crosslinkable macromolecules in the entire rubber system produce a crosslinking network.

Ester plasticizers, epoxy resins and rubber systems have good compatibility and uniform dispersion, which can improve the processing performance of the system; epoxy resin is a non-degradable substance, after the degradation of the blend system, the epoxy resin shrinks and gathers degradation residues, After a long period of time, the epoxy resin and the degradation residue will solidify, which is easy to concentrate and handle, which is beneficial to environmental protection.

Water, potassium bicarbonate and azobisisobutyronitrile are used as foaming agents to form open-cell sponge during vulcanization; the combination of open-cell sponge structure and starch-based superabsorbent resin can provide high water absorption performance of polyurethane rubber composition .

The polyurethane rubber of the present invention can also adjust the degradation period by adjusting the ratio of polyester type and polyether type polyurethane rubber. After the polyester polyurethane rubber and the polyether polyurethane rubber are hydrophilic, the degradation cycles are different. The polyester type is easy to degrade, and the polyether type is not easy to degrade. The two types of polyurethane rubber are mixed in different proportions, and the degradation cycle of the mixture is different.

In addition, when ammonium persulfate is selected as the initiator and phosphorus-containing inorganic substances are selected as the filler, the polyurethane rubber composition of the present invention can also be used to assist plants in water fixation, and has the effect of increasing fertilizer efficiency and improving soil quality. The composition can produce the fertilizers needed by plants in the water-absorbing state: ammonium persulfate can be decomposed to produce nitrogen-containing fertilizers; phosphorus-containing inorganic substances can be hydrolyzed to produce phosphorus-containing fertilizers. According to the use environment, increasing or decreasing the dosage of granular ordinary calcium superphosphate can Adjust the pH of the environment; Potassium bicarbonate can produce potassium ions.

The characteristics of the present invention are: a. providing a polyurethane rubber composition and its preparation process; b. the polyurethane rubber composition is chemically degradable and biodegradable and has a high water absorption rate. The degradation cycle is 8 to 42 months. It can reach 300-800%; c, the degradation period of the polyurethane rubber composition is 8-42 months, which can be achieved through different proportions of different types of polyurethane rubber and (or) chemical degradation products and (or) biological degradation products. To adjust the degradation cycle; d When used to assist plants in water fixation or improve soil quality, the composition can produce nitrogen, phosphorus and potassium fertilizers required by plants.

Detailed ways

The raw materials used in the following examples are as follows:

Polyester polyurethane rubber: AU28 (Millathane28) Manufacturer: TSX Group Inc;

                                            Manufacturer of HA-1: Shanxi Chemical Research Institute;

S-type rubber 8601 manufacturer: Nanjing Rubber Factory;

Eelastothane 640 Manufacturer: American Thiokol Chemical Company;

Polyether polyurethane rubber: EU26 (Millathane26) Manufacturer: TSX Group Inc;

Starch grafted acrylic resin: XH-10 type, Dalian Synthetic Fiber Research Institute;

Starch grafted acrylonitrile resin: Stasorb 372 type, American Starler Company;

Starch, persulfate, sulfite, stearic acid, zinc oxide, rubber anti-aging agent, filler, ester plasticizer, epoxy resin, foaming agent, rubber crosslinking agent are all commercially available products.

Example 1:

A) firstly, 20 parts by weight of ammonium persulfate are dissolved in 25 parts by weight of deionized water, added into mung bean starch of 100 parts by weight, and stirred evenly to form starch mixture _H1 ;

B) Plasticize 100 parts by weight of polyurethane rubber AU28 on an open mill for 3 minutes, add 25 parts of pre-prepared starch, ammonium persulfate and deionized water mixture H ₁ , knead for 1 minute, add weight parts 1 part of sodium sulfite, after mixing for 5 minutes, add 0.8 parts by weight of stearic acid and 6 parts of zinc oxide, and after mixing for 1 minute, add 35 parts by weight of ammonium phosphate, after mixing for 2 minutes, then Add 15 parts by weight of dioctyl phthalate and 4 parts of bisphenol A type epoxy resin E-44, after mixing for 3 minutes, add 20 parts by weight of XH-10 type starch grafted acrylic resin, Parts by weight are 6 parts of potassium bicarbonate and 3 parts of azobisisobutyronitrile. After mixing for 2 minutes, add 5 parts of dicumyl peroxide and 0.8 parts of auxiliary crosslinking agent sulfur. After mixing for 3 minutes, , Tablet on the open mill.

C) After standing at room temperature for 18 hours, re-mill for 1 minute, put it into a mold, and vulcanize at 160°C with a flat rubber vulcanizer to make a polyurethane rubber composition.

The main performance data are shown in Table 1.

Example 2:

A) First, 6 parts by weight of ammonium persulfate are dissolved in 11 parts by weight of deionized water, added to 100 parts by weight of wheat starch, and stirred evenly to form a starch mixture H ₂ ;

B) Plasticize 100 parts by weight of polyurethane rubber EU26 on an internal mixer for 2 minutes, add 12 parts of pre-prepared starch, ammonium persulfate and deionized water mixture H ₂ , knead for 1 minute, add weight parts 0.6 parts of potassium sulfite, after mixing for 6 minutes, add 1 part by weight of stearic acid and 8 parts of zinc oxide, and after mixing for 1 minute, add 1.5 parts by weight of N-(1,3- Dimethylbutyl)-N'-phenyl-p-phenylenediamine organic complex and 1 part of 2-mercaptobenzimidazole, after mixing for 1 minute, adding weight parts is 48 parts of granular common calcium superphosphate, mixing After refining for 3 minutes, add 10 parts of dioctyl sebacate and 7 parts of bisphenol A type epoxy resin E-42 in parts by weight, and then add 31 parts of Stasorb 372 type starch in parts by weight after mixing for 3 minutes. Acrylonitrile resin, 8 parts of ammonium bicarbonate and 2 parts of N, N'-dinitrosopentamethylenetetramine, after mixing for 4 minutes, add 6 parts of dicumyl peroxide and 0.5 parts of Auxiliary cross-linking agent triallyl isocyanurate, after mixing for 4 minutes, press on the open mill.

C) After standing at room temperature for 18 hours, re-mill for 1 minute, put it into a mold, and vulcanize it at 170°C with a flat rubber vulcanizer to make a polyurethane rubber composition.

The main performance data are shown in Table 1.

Example 3:

A) at first the ammonium persulfate that is 8 parts by weight is dissolved in the deionized water that is 15 parts by weight, joins in the potato starch that is 100 parts by weight, stirs evenly, forms starch mixture H ₃ ;

B) The polyurethane rubber EU26 that is 50 parts by weight is masticated on the open mill for 2 minutes, and then the polyurethane rubber AU 28 that is 50 parts by weight is added to the open mill and mixed with polyurethane rubber Eelastothane 640 for 3 minutes, and 35 parts are added Parts of pre-prepared starch, sodium persulfate and deionized water mixture H ₃ , after kneading for 1 minute, add 0.7 parts by weight of potassium sulfite, and after kneading for 8 minutes, add 0.9 parts by weight of stearic acid And 5.6 parts of zinc oxide, after mixing for 1 minute, add the N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine organic complex of 2.4 parts by weight, and mix After 0.5 minutes, add 40 parts by weight of tricalcium phosphate, and after mixing for 1 minute, add 7 parts of dioctyl adipate, 5 parts of dioctyl phthalate and 16 parts of bisphenol A epoxy resin E-44, after mixing for 2 minutes, add 33 parts by weight of Stasorb 372 type starch grafted acrylonitrile resin, 10 parts of potassium borohydride and 2 parts of azobisisobutyronitrile, after mixing for 3 minutes, add weight The parts are 3 parts of dicumyl peroxide, 1.5 parts of sulfur and 0.5 part of dibenzothiazole disulfide, and after mixing for 5 minutes, they are compressed on an open mill.

C) After standing at room temperature for 18 hours, re-mill for 2 minutes, put it into a mold, vulcanize at 165°C with a flat rubber vulcanizer, and make a polyurethane rubber composition.

The main performance data are shown in Table 1.

Example 4:

A) At first, 3 parts by weight of potassium persulfate are dissolved in 32 parts by weight of deionized water, added into 38 parts by weight of bean starch and 62 parts of potato starch, stirred evenly to form starch mixture _H4 ;

B) the polyurethane rubber EU26 that is 30 parts by weight is masticated on the open mill for 3 minutes, and then the polyurethane rubber AU 28 that is 70 parts by weight is added to the open mill and mixed with HA-1 type polyurethane rubber for 2 minutes, Add 53 parts of pre-prepared starch, ammonium persulfate and deionized water mixture H ₄ , after kneading for 2 minutes, add 4 parts by weight of ammonium sulfite, and after kneading for 10 minutes, add 2.5 parts by weight of hard Fatty acid and 12 parts of zinc oxide, after kneading for 2 minutes, add 0.7 parts of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1.2 parts of N, N'-di(2-octyl)-p-phenylenediamine, after mixing for 1 minute, add 60 parts by weight of superfine calcium carbonate, and after mixing for 3 minutes, add 13 parts by weight of trioctyl phosphate , 30 parts of dioctyl phthalate, 16 parts of bisphenol A epoxy resin E-44 and 11 parts of bisphenol A epoxy resin E-42, after mixing for 5 minutes, add 40 parts by weight XH-10 starch-based superabsorbent resin, 10 parts by weight of azobisisobutyronitrile and 7 parts of ammonium carbonate, after mixing for 2 minutes, add 10 parts by weight of dibenzoyl peroxide, 1.5 parts by weight Tetramethylthiuram disulfide and 1.5 parts of N-cyclohexyl-2-benzothiazole sulfenamide were kneaded for 4 minutes and then compressed on an open mill.

C) After standing at room temperature for 24 hours, re-mill for 5 minutes, put it into a mold, vulcanize at 175°C with a flat rubber vulcanizer, and make a polyurethane rubber composition.

The main performance data are shown in Table 1.

Example 5:

A) First, 14 parts by weight of ammonium persulfate are dissolved in 30 parts by weight of deionized water, added into 38 parts by weight of bean starch and 62 parts of potato starch, stirred evenly to form starch mixture _H5 ;

B) the polyurethane rubber EU26 that is 70 parts by weight is masticated on the open mill for 2 minutes, and then the polyurethane rubber AU 28 that is 30 parts by weight is added to the open mill and mixed with S-type 8601 type polyurethane rubber for 2 minutes, Add 16 parts of pre-prepared starch, ammonium persulfate and deionized water mixture H ₅ , after kneading for 2 minutes, add 2.1 parts by weight of ammonium sulfite, and after kneading for 10 minutes, add 1.3 parts by weight of hard Fatty acid and 5 parts of zinc oxide, after kneading for 2 minutes, add 0.5 parts of 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2 parts of N-isopropyl Base-N'-phenyl-p-phenylenediamine, after mixing for 1 minute, add 10 parts by weight of white carbon black, and after mixing for 5 minutes, add 22 parts by weight of tributyrin, 10 parts of bis Phenol A type epoxy resin E-42, after mixing for 3 minutes, add 56 parts by weight of XH-10 type starch-based superabsorbent resin, 7 parts of ammonium carbonate, and after mixing for 2 minutes, add 8 parts by weight 1 part of tetramethylthiuram disulfide, 0.5 part of sulfur and 1.5 part of 2-mercaptobenzothiazole dimethyl ammonium salt, mixed for 4 minutes, and then compressed on an open mill.

C) After standing at room temperature for 24 hours, re-mill for 5 minutes, put it into a mold, and vulcanize at 170° C. with a flat rubber vulcanizer to make a polyurethane rubber composition.

The main performance data are shown in Table 1.

Table 1 embodiment main performance data

Claims (15)

1. a polyurethane rubber composition is 100 weight parts in polyester type and/or the mixing urethanes of polyether-type, comprises following component:

The mixing urethanes of polyester type and/or polyether-type, 100 parts;

Starch, persulphate and water mixture are designated as H, and 10～60 parts, wherein the proportioning of starch, persulphate and water is 100: (2～20): (10～35) in weight part;

Sulphite, 0.5～5 part;

Triple Pressed Stearic Acid, 0.5～3 part;

Zinc oxide, 3～15 parts;

Rubber antioxidant, 0～5 part;

Weighting agent, 5～70 parts;

Ester plasticizer, 5～50 parts;

Epoxy resin, 1～30 part;

Starch is super absorbent resin, 15～60 parts;

Whipping agent, 1～20 part;

A rubber crosslinker, 3～15 parts;

Described whipping agent is selected from water, saleratus, volatile salt, bicarbonate of ammonia, sodium hydrogencarbonate, POTASSIUM BOROHYDRIDE 97MIN, Diisopropyl azodicarboxylate, N, N '-dinitroso five methyne tetramines.

2. polyurethane rubber composition as claimed in claim 1, when it is characterized in that polyester type and polyether types of polyurethane rubber are shared, the two ratio can be adjusted arbitrarily.

3. polyurethane rubber composition as claimed in claim 1 is characterized in that described starch is selected from one or more in beans ative starch, wheat class ative starch, rice kind of starch, cereal ative starch or the potato class ative starch.

4. polyurethane rubber composition as claimed in claim 1 is characterized in that described persulphate is selected from the alkaline earth salt of an alkali metal salt of persulfuric acid, persulfuric acid or the non-metal salt of persulfuric acid.

5. polyurethane rubber composition as claimed in claim 1 is characterized in that described rubber antioxidant is selected from one or more in amines antioxidants, phenols and verivate anti-aging agent thereof or the benzimidazoles anti-aging agent.

6. polyurethane rubber composition as claimed in claim 5; It is characterized in that described rubber antioxidant is selected from N; N '-two (2-octyl group)-Ursol D, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N; N '-two (1,4-dimethyl-amyl group)-Ursol D, N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine organic complex, 3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, 2, two or more in 2 '-sulfo-two (4-methyl-6-tert butyl phenol), the 2-mercaptobenzimidazole.

7. polyurethane rubber composition as claimed in claim 1 is characterized in that described weighting agent is that inorganic phosphor-contained thing is selected from ammonium phosphate, superphosphate of lime, tricalcium phosphate, double superhosphate.

8. polyurethane rubber composition as claimed in claim 1 is characterized in that described weighting agent is that inorganic filler is selected from WHITE CARBON BLACK, talcum powder, lime carbonate, Natural manganese dioxide.

9. polyurethane rubber composition as claimed in claim 1 is characterized in that described ester plasticizer is selected from one or more in phthalate, aliphatic dibasic acid ester, phosphoric acid ester, fatty acid ester or the polyol ester.

10. polyurethane rubber composition as claimed in claim 1 is characterized in that described epoxy resin is the bisphenol A type epoxy resin that is liquid under the normal temperature.

11. polyurethane rubber composition as claimed in claim 1 is characterized in that described starch is that super absorbent resin can be starch-grafted acrylonitrile resin or starch graft acrylic acid resin.

12. polyurethane rubber composition as claimed in claim 1 is characterized in that described a rubber crosslinker is made up of main linking agent and additional crosslinker, the quality proportioning of main linking agent and additional crosslinker is: (3～10): (0.1～5).

13. polyurethane rubber composition as claimed in claim 12 is characterized in that described a rubber crosslinker master linking agent is the organo-peroxide class, additional crosslinker is selected from sulphur or contains in the sulfur donor compound one or more.

14. polyurethane rubber composition as claimed in claim 12; It is characterized in that described a rubber crosslinker master linking agent is a kind of in sulphur or the sulfur-bearing sulfur donor compound, additional crosslinker is one or more in thiazoles, thiurams or the sulfenamide.

15. the preparation method of a rubber combination as claimed in claim 1 is characterized in that:

(1) at first prepare the mixture of starch and persulphate and water, high-speed stirring made starch, persulphate and water mix in 5～30 minutes, formed mixture H;

(2) urethanes was plasticated 1～5 minute in mill or Banbury mixer after, in mill or Banbury mixer, add preprepared mixture H, after mixing 1～5 minute, add sulphite; In mill or Banbury mixer, reacted 4～10 minutes, and made starch partially grafted on polyurethane molecular, add Triple Pressed Stearic Acid and zinc oxide afterwards; After mixing 1～5 minute, add rubber antioxidant, after mixing 1～3 minute; Add weighting agent, after mixing 2～5 minutes, add ester plasticizer and epoxy resin again; After mixing 2～8 minutes, adding starch again is super absorbent resin and whipping agent, after mixing 1～5 minute; Add a rubber crosslinker, after mixing 2～6 minutes, compressing tablet in mill;

(3) park 12～24 hours under the room temperature after, 130～180 ℃ down the sulfuration back use.