CN101824217A - Polyurethane rubber composition and preparation process thereof - Google Patents
Polyurethane rubber composition and preparation process thereof Download PDFInfo
- Publication number
- CN101824217A CN101824217A CN200910079179A CN200910079179A CN101824217A CN 101824217 A CN101824217 A CN 101824217A CN 200910079179 A CN200910079179 A CN 200910079179A CN 200910079179 A CN200910079179 A CN 200910079179A CN 101824217 A CN101824217 A CN 101824217A
- Authority
- CN
- China
- Prior art keywords
- starch
- parts
- rubber composition
- polyurethane rubber
- mixing
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a degradable polyurethane rubber composition with high water absorbability and a preparation process thereof. The rubber composition has both high water absorbability and biodegradability. Based on 100 parts by weight of polyester and/or polyether mixed polyurethane rubber, the polyurethane rubber composition comprises the following components: 100 parts of polyester and/or polyether mixed polyurethane rubber, 10 to 60 parts of mixture of starch, persulfate and water, 15 to 60 parts of starch series resin with high water absorbability, and other auxiliary agents. The degradable polyurethane rubber composition can be chemically degraded and biologically degraded, and has high water absorbability; and the degradation cycle can be adjusted through different matches of polyurethane rubbers of different types and/or matches of chemical degradation substances and/or biological degradation substances, the degradation cycle is 8 to 42 months, and the swelling multiplying power in distilled water is 300 to 800 percent.
Description
Technical field
The present invention relates to have the degradable polyurethane rubber combination of excellent biodegradability and chemical degradation ability and the preparation technology of described rubber combination.
Background technology
Along with era development, great variety has taken place in whole world rubber industry, the cross-linked rubber of tradition vulcanization of rubber complete processing manufacturing is after losing use properties, be difficult for degraded, brought a large amount of rubbish to human habitat, thereby everybody wishes to use a kind of cross-linked rubber masses that can degrade after the use properties that loses.CN1563155A discloses a kind of hydro-expansive rubber by water uptake expansion resin preparation and preparation method thereof.Wherein water uptake expansion resin is polymerized in proportion by the polymerization single polymerization monomer, catalyzer, initiator and the linking agent that contain Soxylat A 25-7 (methyl) acrylate; Hydro-expansive rubber is formed by mixing, sulfuration by water uptake expansion resin, neoprene latex, weighting agent, tenderizer, promotor and anti-aging agent, and this hydro-expansive rubber excellent property is anti-ionic good, does not have precipitate behind the chance water.Its parts by weight are, water uptake expansion resin is that 50～100 parts, neoprene latex are that 100 parts, weighting agent are that 20～35 parts, tenderizer are that 10～20 parts, promotor are that 0.5～1.0 part, anti-aging agent are 0.5～1.0 part.The disclosed hydro-expansive rubber vulcanising composition of the document mainly uses neoprene latex, hydro-expansive rubber vulcanising composition non-degradable.
Summary of the invention
The object of the present invention is to provide degradable polyurethane rubber composition of a kind of high-hydroscopicity and preparation method thereof, make this rubber combination when having high-hydroscopicity, have degradability concurrently.
A kind of 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 (weight part) is 100: (2～20): (10～35);
Sulphite, 0.5～5 part;
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;
Resins, epoxy, 1～30 part;
Starch is super absorbent resin, 15～60 parts;
Whipping agent, 1～20 part;
A rubber crosslinker, 3～15 parts.
Urethanes of the present invention is the commercially available prod, Polyester based Polyurethane Rubber(ASTM) such as AU28 (Millathane28), polyester type HA-1, S type glue, Eelastothane 640 etc.; Polyether types of polyurethane rubber such as EU26 (Millathane26), when wherein polyester type and polyether types of polyurethane rubber were shared, the two ratio can be adjusted arbitrarily.
Used starch can be one or more in beans ative starch, wheat class ative starch, rice kind of starch, cereal ative starch or the potato class ative starch.
The used persulphate of the present invention can be an alkali metal salt such as Potassium Persulphate, the Sodium Persulfate etc. of persulfuric acid, or the alkaline earth salt of persulfuric acid such as persulfuric acid calcium etc., also can be the non-metal salt of persulfuric acid such as ammonium persulphate etc.
Sulphite is water-soluble, and institute's cation can be non-oxidative metal ion in the sulphite, also can be non-oxidizable nonmetallic ion (group), metal ion such as sodium ion, potassium ion etc., nonmetallic ion such as ammonium radical ion etc.
Rubber antioxidant of the present invention can be one or more in amines antioxidants, phenols (derivative) anti-aging agent or the benzimidazoles anti-aging agent.
Described amines antioxidants 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 etc.
Described phenols (derivative) anti-aging agent is selected from 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, 2,2 '-sulfo-two (4-methyl-6-tert butyl phenol) etc.
Described benzimidazoles anti-aging agent such as 2-mercaptobenzimidazole etc.
Described weighting agent can be that inorganic phosphor-contained thing is selected from ammonium phosphate, calcium superphosphate, tricalcium phosphate, double superhosphate etc., also can be that other inorganic filler is selected from white carbon black, talcum powder, lime carbonate, magnesium oxide etc.
Ester plasticizer of the present invention can be one or more in phthalate, aliphatic dibasic acid ester, phosphoric acid ester, fatty acid ester or the polyol ester.
Resins, epoxy of the present invention is bisphenol A type epoxy resin such as E-44, the E-42 etc. that are liquid under the normal temperature, or the mixture of above-mentioned Resins, epoxy.
Starch of the present invention is that super absorbent resin can be starch-grafted acrylonitrile resin or starch graft acrylic acid resin.
Whipping agent of the present invention can be mineral-type foaming agent for opening aperture such as water, saleratus, volatile salt, bicarbonate of ammonia, sodium bicarbonate, POTASSIUM BOROHYDRIDE etc., also can be organic class foaming agent for opening aperture such as Diisopropyl azodicarboxylate, N, N '-dinitroso five methyne tetramines etc., or the mixture of above-mentioned mineral-type foaming agent for opening aperture and organic class foaming agent for opening aperture.
A rubber crosslinker of the present invention is made up of main linking agent and additional crosslinker, and the proportioning of main linking agent and additional crosslinker (in weight part) is: (3～10): (0.1～5).Main linking agent can be the organo-peroxide class, a kind of as in dicumyl peroxide, the dibenzoyl peroxide etc., at this moment additional crosslinker can be sulphur, contain the morpholine derivative of sulfur donor compound such as thiurams, sulfur-bearing, in the iso-cyanuric acid triallyl ester one or more; Main linking agent also can be a kind of in sulphur or the sulfur-bearing sulfur donor compound, and at this moment additional crosslinker can be one or more in thiazoles, thiurams or the sulfenamide.
Rubber combination of the present invention prepares by the following method:
(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, make starch partially grafted on polyurethane molecular, add 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 Resins, epoxy again, after mixing 2～8 minutes, adding starch again is super absorbent resin and whipping agent, after mixing 1～5 minute, adds 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.
Persulphate that the present invention added and sulphite have been formed the initiator system of starch-grafted urethanes, starch reacts with blending-type polyurethane under the effect of initiator system, make starch partially grafted on polyurethane molecular, form the increase-volume interface, can increase starch is the consistency of super absorbent resin and rubber mix objects system, and residue there is not grafted starch then to can be used as degradable system biological degradation point.
The stearic acid that is added, zinc oxide form vulcanization system as vulcanization leveller with linking agent and additional crosslinker, can make crosslinkable macromole generation cross-linked network in the whole rubbery system with the urethanes effect.
Ester plasticizer, Resins, epoxy and rubbery system consistency are good, are uniformly dispersed, and can improve the system processing characteristics; Resins, epoxy is the non-degradable thing, and after the co-mixing system degraded, Resins, epoxy shrinks assembles the degrade residual thing, and after long-time, Resins, epoxy and the effect of degrade residual thing are solidified, and are easy to focus on, and are beneficial to environment protection.
Water, saleratus and Diisopropyl azodicarboxylate etc. use as whipping agent, form porous sponge in sulfidation; Porous sponge structure and starch are the high-hydroscopicity energy that the super absorbent resin combination can provide polyurethane rubber composition.
Urethanes of the present invention can also be regulated degradation cycle by the ratio of regulating polyester type and polyether types of polyurethane rubber.After Polyester based Polyurethane Rubber(ASTM) and polyether types of polyurethane rubber itself is hydrophilic, the degradation cycle difference, the easy degraded of polyester type, the difficult degraded of polyether-type, two kinds of urethaness are pressed different ratios and are mixed the degradation cycle difference of mixture.
In addition, when selecting for use ammonium persulphate as initiator, when selecting inorganic phosphor-contained thing for use as weighting agent, polyurethane rubber composition of the present invention can also be used for auxiliary plant solid water, have the effect that increases fertilizer efficiency and improve the soil soil property, said composition can produce the required fertilizer of plant under the suction state: ammonium persulphate decomposes can produce nitrogenous fertilizer; Inorganic phosphor-contained thing hydrolyzable goes out to contain phosphatic manure, and according to environment for use, the consumption that increases or reduce granulated common calcium superphosphate can be regulated the environment potential of hydrogen; Saleratus can produce potassium ion.
Characteristics of the present invention are: a provides a kind of polyurethane rubber composition and preparation technology thereof; But this polyurethane rubber composition chemical degradation of b and biological degradation and water-intake rate height, degradation cycle is 8～42 months, expansion multiplying power can reach 300～800% in distilled water; The degradation cycle of this polyurethane rubber composition of c is 8～42 months, different proportionings that can be by the different model urethanes and (or) the chemical degradation thing and (or) proportioning of biological degradation thing regulates degradation cycle; When d was used for auxiliary plant solid water or improves the soil soil property, said composition can produce the required NPK fertilizers of plant.
Embodiment
The employed raw material of following examples is as follows:
Polyester based Polyurethane Rubber(ASTM): AU28 (Millathane28) type producer: TSX Group Inc;
HA-1 type producer: Shanxi-Prov Inst of Chemical Industry;
S type glue 8601 type producers: Nanjing rubber plant;
Eelastothane 640 producers: U.S. Thiokol chemical company;
Polyether types of polyurethane rubber: EU26 (Millathane26) type producer: TSX Group Inc;
Starch graft acrylic acid resin: XH-10 type, Dalian Synthetic Fibres Inst.;
Starch-grafted acrylonitrile resin: Stasorb 372 types, U.S. Starler company;
Starch, persulphate, sulphite, stearic acid, zinc oxide, rubber antioxidant, weighting agent, ester plasticizer, Resins, epoxy, whipping agent, a rubber crosslinker are the commercially available prod.
Embodiment 1:
A) at first be with weight part 20 parts ammonium persulphate to be dissolved in weight part be in 25 parts the deionized water, join weight part and be in 100 parts the green starch, stir, form starch mixture H
1
B) be that 100 parts urethanes AU28 plasticated in mill 3 minutes with weight part, add 25 parts of preprepared starch and ammonium persulphate and deionized water mixture H
1After mixing 1 minute, adding weight part is 1 part of S-WAT, after mixing 5 minutes, adding weight part is 0.8 part stearic acid and 6 parts zinc oxide, after mixing 1 minute, adding weight part is 35 parts of ammonium phosphate, and after mixing 2 minutes, adding weight part again is 15 parts of dioctyl phthalate (DOP)s and 4 parts of bisphenol A type epoxy resin E-44, after mixing 3 minutes, adding weight part again is 20 parts of XH-10 type starch graft acrylic acid resins, weight part is 6 parts of saleratus and 3 parts of Diisopropyl azodicarboxylates, and after mixing 2 minutes, adding weight part is 5 parts of dicumyl peroxides and 0.8 part of additional crosslinker sulphur, after mixing 3 minutes, compressing tablet in mill.
C) at room temperature park 18 hours after, mould is put in back mixing 1 minute again, at 160 ℃ down after the sulfuration, makes polyurethane rubber composition with dull and stereotyped rubber vulcanizing machine.
The salient features data see Table 1.
Embodiment 2:
A) at first be with weight part 6 parts ammonium persulphate to be dissolved in weight part be in 11 parts the deionized water, join weight part and be in 100 parts the wheat starch, stir, form starch mixture H
2
B) be that 100 parts urethanes EU26 plasticated on Banbury mixer 2 minutes with weight part, add 12 parts of preprepared starch and ammonium persulphate and deionized water mixture H
2After mixing 1 minute, adding weight part is 0.6 part of potassium sulfite, after mixing 6 minutes, adding weight part is 1 part stearic acid and 8 parts zinc oxide, after mixing 1 minute, the adding weight part is 1.5 parts N-(1, the 3-dimethylbutyl)-2-mercaptobenzimidazole of N '-diphenyl-para-phenylene diamine organic complex and 1 part, after mixing 1 minute, adding weight part is 48 parts of granulated common calcium superphosphates, after mixing 3 minutes, adding weight part again is 10 parts of dioctyl sebacates and 7 parts of bisphenol A type epoxy resin E-42, after mixing 3 minutes, adding weight part again is 31 parts of starch-grafted acrylonitrile resins of Stasorb 372 types, 8 parts of bicarbonate of ammonia and 2 parts of N, N '-dinitroso five methyne tetramines, after mixing 4 minutes, adding weight part is 6 parts of dicumyl peroxides and 0.5 part of additional crosslinker iso-cyanuric acid triallyl ester, after mixing 4 minutes, compressing tablet in mill.
C) at room temperature park 18 hours after, mould is put in back mixing 1 minute again, at 170 ℃ down after the sulfuration, makes polyurethane rubber composition with dull and stereotyped rubber vulcanizing machine.
The salient features data see Table 1.
Embodiment 3:
A) at first be with weight part 8 parts ammonium persulphate to be dissolved in weight part be in 15 parts the deionized water, join weight part and be in 100 parts the sweet potato starch, stir, form starch mixture H
3
B) be that 50 parts urethanes EU26 plasticated in mill 2 minutes with weight part, be that 50 parts urethanes AU 28 adds mills and mixes with urethanes Eelastothane 640 and plasticate 3 minutes again with weight part, add 35 parts of preprepared starch and Sodium Persulfate and deionized water mixture H
3After mixing 1 minute, adding weight part is 0.7 part of potassium sulfite, after mixing 8 minutes, adding weight part is 0.9 part stearic acid and 5.6 parts zinc oxide, after mixing 1 minute, the adding weight part is 2.4 parts N-(1, the 3-dimethylbutyl)-and N '-diphenyl-para-phenylene diamine organic complex, after mixing 0.5 minute, adding weight part is 40 parts of tricalcium phosphates, after mixing 1 minute, add 7 parts of Octyl adipates again, 5 parts of dioctyl phthalate (DOP)s and 16 parts of bisphenol A type epoxy resin E-44, after mixing 2 minutes, adding weight part again is 33 parts of starch-grafted acrylonitrile resins of Stasorb 372 types, 10 parts of POTASSIUM BOROHYDRIDE and 2 parts of Diisopropyl azodicarboxylates, after mixing 3 minutes, adding weight part is 3 parts of dicumyl peroxides, 1.5 part sulphur and 0.5 part of dibenzothiazyl disulfide, after mixing 5 minutes, compressing tablet in mill.
C) at room temperature park 18 hours after, mould is put in back mixing 2 minutes again, at 165 ℃ down after the sulfuration, makes polyurethane rubber composition with dull and stereotyped rubber vulcanizing machine.
The salient features data see Table 1.
Embodiment 4:
A) at first be with weight part 3 parts Potassium Persulphate to be dissolved in weight part be in 32 parts the deionized water, join weight part and be in the yam starch of 38 parts beans ative starch and 62 parts, stir, form starch mixture H
4
B) be that 30 parts urethanes EU26 plasticated in mill 3 minutes with weight part, the urethanes AU 28 adding mills and the HA-1 type polyurethane rubber mix that with weight part are 70 parts were again plasticated 2 minutes, added 53 parts of preprepared starch and ammonium persulphate and deionized water mixture H
4After mixing 2 minutes, adding weight part is 4 parts of ammonium sulphites, after mixing 10 minutes, adding weight part is 2.5 parts stearic acid and 12 parts zinc oxide, after mixing 2 minutes, the adding weight part is 0.7 part 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and 1.2 parts of N, N '-two (2-octyl group)-Ursol D, after mixing 1 minute, adding weight part is 60 parts of calcium carbonate superfine powders, and after mixing 3 minutes, adding weight part again is 13 parts of trioctyl phosphates, 30 parts of dioctyl phthalate (DOP)s, 16 parts of bisphenol A type epoxy resin E-44 and 11 parts of bisphenol A type epoxy resin E-42, after mixing 5 minutes, adding weight part again is that 40 parts of XH-10 type starch are super absorbent resin, weight part is 10 parts of Diisopropyl azodicarboxylates and 7 parts of volatile salts, and after mixing 2 minutes, the adding weight part is 10 parts and crosses dibenzoyl peroxide, 1.5 part tetramethyl thiuram disulfide and 1.5 parts of N cyclohexyl 2 benzothiazole sulfenamides, after mixing 4 minutes, compressing tablet in mill.
C) at room temperature park 24 hours after, mould is put in back mixing 5 minutes again, at 175 ℃ down after the sulfuration, makes polyurethane rubber composition with dull and stereotyped rubber vulcanizing machine.
The salient features data see Table 1.
Embodiment 5:
A) at first be with weight part 14 parts ammonium persulphate to be dissolved in weight part be in 30 parts the deionized water, join weight part and be in the yam starch of 38 parts beans ative starch and 62 parts, stir, form starch mixture H
5
B) be that 70 parts urethanes EU26 plasticated in mill 2 minutes with weight part, the urethanes AU 28 adding mills and the S type 8601 type polyurethane rubber mix that with weight part are 30 parts were again plasticated 2 minutes, added 16 parts of preprepared starch and ammonium persulphate and deionized water mixture H
5After mixing 2 minutes, adding weight part is 2.1 parts of ammonium sulphites, after mixing 10 minutes, adding weight part is 1.3 parts stearic acid and 5 parts zinc oxide, after mixing 2 minutes, add weight part and be 0.5 part 2,2 '-sulfo-two (4-methyl-6-tert butyl phenol) and 2 parts of N-sec.-propyl-N '-diphenyl-para-phenylene diamines, after mixing 1 minute, adding weight part is 10 parts of white carbon blacks, after mixing 5 minutes, adding weight part again is 22 parts of tributyrins, 10 parts of bisphenol A type epoxy resin E-42, after mixing 3 minutes, adding weight part again is that 56 parts of XH-10 type starch are super absorbent resin, 7 parts of volatile salts, after mixing 2 minutes, adding weight part is 8 parts of tetramethyl thiuram disulfides, 0.5 part sulphur and 1.5 parts of 2-mercaptobenzothiazole dimethyl ammoniums, after mixing 4 minutes, compressing tablet in mill.
C) at room temperature park 24 hours after, mould is put in back mixing 5 minutes again, at 170 ℃ down after the sulfuration, makes polyurethane rubber composition with dull and stereotyped rubber vulcanizing machine.
The salient features data see Table 1.
Table 1 embodiment salient features data
Claims (17)
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 (weight part) is 100: (2～20): (10～35);
Sulphite, 0.5～5 part;
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;
Resins, epoxy, 1～30 part;
Starch is super absorbent resin, 15～60 parts;
Whipping agent, 1～20 part;
A rubber crosslinker, 3～15 parts.
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 derivative 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, calcium superphosphate, 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, magnesium oxide.
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 Resins, epoxy 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 whipping agent is selected from mineral-type foaming agent for opening aperture, organic class foaming agent for opening aperture.
13. polyurethane rubber composition as claimed in claim 12 is characterized in that described whipping agent is selected from water, saleratus, volatile salt, bicarbonate of ammonia, sodium bicarbonate, POTASSIUM BOROHYDRIDE, Diisopropyl azodicarboxylate, N, N '-dinitroso five methyne tetramines.
14. 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).
15. polyurethane rubber composition as claimed in claim 14 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.
16. polyurethane rubber composition as claimed in claim 14, 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.
17. 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, make starch partially grafted on polyurethane molecular, add 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 Resins, epoxy again, after mixing 2～8 minutes, adding starch again is super absorbent resin and whipping agent, after mixing 1～5 minute, adds 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100791793A CN101824217B (en) | 2009-03-04 | 2009-03-04 | Polyurethane rubber composition and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100791793A CN101824217B (en) | 2009-03-04 | 2009-03-04 | Polyurethane rubber composition and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101824217A true CN101824217A (en) | 2010-09-08 |
| CN101824217B CN101824217B (en) | 2012-01-11 |
Family
ID=42688396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100791793A Active CN101824217B (en) | 2009-03-04 | 2009-03-04 | Polyurethane rubber composition and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101824217B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206364A (en) * | 2011-01-27 | 2011-10-05 | 江阴海达橡塑股份有限公司 | Method for preparing water-swellable rubber |
| CN103497361A (en) * | 2013-09-29 | 2014-01-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of thermoplastic starch material based on non-grain woody plant oil and fat |
| CN106084740A (en) * | 2016-08-16 | 2016-11-09 | 苏州市云林电子有限公司 | A kind of high-performance modified polyurethane rubber |
| CN106105452A (en) * | 2016-07-30 | 2016-11-16 | 山东胜伟园林科技有限公司 | A kind of method using erosion-resisting hidden pipe to carry out salt discharge and the application in alkaline land improving thereof |
| TWI582166B (en) * | 2016-06-30 | 2017-05-11 | 財團法人鞋類暨運動休閒科技研發中心 | Tpu foam material and foams thereof |
| CN108219224A (en) * | 2018-01-24 | 2018-06-29 | 茂联橡胶制品（深圳）有限公司 | Compounded rubber and preparation method thereof |
| CN108239382A (en) * | 2016-12-27 | 2018-07-03 | 北京橡胶工业研究设计院有限公司 | A kind of polyurethane rubber composition for track flaw detection wheel case |
| CN108841166A (en) * | 2018-07-11 | 2018-11-20 | 安徽嘉明新材料科技有限公司 | A kind of degradable TPU packaging film |
| CN110016224A (en) * | 2019-04-22 | 2019-07-16 | 东莞方德泡绵制品厂有限公司 | A kind of formula and its manufacture craft of environment-friendly foaming cotton |
| CN110294876A (en) * | 2014-03-07 | 2019-10-01 | 株式会社吴羽 | Drilling tool decomposability rubber component and decomposability containment member |
| CN114907683A (en) * | 2021-12-13 | 2022-08-16 | 中昊黑元化工研究设计院有限公司 | Preparation method of soluble bridge plug rubber material for shale gas exploitation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4335231A (en) * | 1981-04-03 | 1982-06-15 | Uniroyal, Inc. | Sulfur curable millable polyurethane gum |
| CN1267487C (en) * | 2004-08-23 | 2006-08-02 | 成都新柯力化工科技有限公司 | Biodegradation starch resin masterbatch |
-
2009
- 2009-03-04 CN CN2009100791793A patent/CN101824217B/en active Active
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206364A (en) * | 2011-01-27 | 2011-10-05 | 江阴海达橡塑股份有限公司 | Method for preparing water-swellable rubber |
| CN103497361A (en) * | 2013-09-29 | 2014-01-08 | 中国林业科学研究院林产化学工业研究所 | Preparation method of thermoplastic starch material based on non-grain woody plant oil and fat |
| CN103497361B (en) * | 2013-09-29 | 2015-09-02 | 中国林业科学研究院林产化学工业研究所 | Based on the preparation method of the thermoplastic starch material of non-grain xylophyta grease |
| CN110294876A (en) * | 2014-03-07 | 2019-10-01 | 株式会社吴羽 | Drilling tool decomposability rubber component and decomposability containment member |
| CN110294876B (en) * | 2014-03-07 | 2021-09-21 | 株式会社吴羽 | Degradable rubber member for drilling tool and degradable sealing member |
| TWI582166B (en) * | 2016-06-30 | 2017-05-11 | 財團法人鞋類暨運動休閒科技研發中心 | Tpu foam material and foams thereof |
| CN106105452A (en) * | 2016-07-30 | 2016-11-16 | 山东胜伟园林科技有限公司 | A kind of method using erosion-resisting hidden pipe to carry out salt discharge and the application in alkaline land improving thereof |
| CN106084740A (en) * | 2016-08-16 | 2016-11-09 | 苏州市云林电子有限公司 | A kind of high-performance modified polyurethane rubber |
| CN108239382A (en) * | 2016-12-27 | 2018-07-03 | 北京橡胶工业研究设计院有限公司 | A kind of polyurethane rubber composition for track flaw detection wheel case |
| CN108219224A (en) * | 2018-01-24 | 2018-06-29 | 茂联橡胶制品（深圳）有限公司 | Compounded rubber and preparation method thereof |
| CN108219224B (en) * | 2018-01-24 | 2020-05-19 | 茂联橡胶制品（深圳）有限公司 | Composite rubber and preparation method thereof |
| CN108841166A (en) * | 2018-07-11 | 2018-11-20 | 安徽嘉明新材料科技有限公司 | A kind of degradable TPU packaging film |
| CN110016224A (en) * | 2019-04-22 | 2019-07-16 | 东莞方德泡绵制品厂有限公司 | A kind of formula and its manufacture craft of environment-friendly foaming cotton |
| CN114907683A (en) * | 2021-12-13 | 2022-08-16 | 中昊黑元化工研究设计院有限公司 | Preparation method of soluble bridge plug rubber material for shale gas exploitation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101824217B (en) | 2012-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101824217B (en) | Polyurethane rubber composition and preparation process thereof | |
| CN109535670B (en) | Full-degradable simulation material and preparation method thereof | |
| CN104559087A (en) | Controllable bio-based full-degradable mulching film | |
| CN102417648A (en) | Biodegradable polyethylene plastic film | |
| CN108359224A (en) | A kind of degradable mulch and preparation method thereof with slow-release nitrogen fertilizer | |
| CN102786734B (en) | Composite foamed shoe material formed by polyolefin and polyolefin elastomers grafted with starch in dry process | |
| CN109181090A (en) | Dedicated Degradable environment protection mulch of milpa and preparation method thereof | |
| CN104530596B (en) | A kind of method utilizing activated sludge to produce degradation plastic | |
| CN111499829A (en) | Environment-friendly odorless foaming sole material and method for preparing sole by using same | |
| CN101418085A (en) | Natural rubber sole and preparation method thereof | |
| CN101298393A (en) | Potassium sulfate and magnesium sulfate fertilizer production process having extrusion prilling step and no drying step | |
| CN112940389A (en) | Anaerobic degradation material and preparation method thereof | |
| CN113999502B (en) | anti-UV (ultraviolet) aging biodegradable mulching film and preparation method thereof | |
| CN107245016A (en) | A kind of organic/inorganic compound fertilizer material and its manufacture method | |
| CN107586164A (en) | A kind of rice special bio functional form bacterial manure and its manufacture method | |
| CN110527146A (en) | A kind of degradable sorting rubbish bag and preparation method thereof | |
| CN101475709B (en) | Preparation of starch foaming body | |
| CN104177202B (en) | Organotrophic saline soil conditioner | |
| CN114854215B (en) | Biodegradable agricultural mulching film modified material and preparation method thereof | |
| CN107057248A (en) | A kind of Degradable environment-friendlyplastic plastic and preparation method thereof | |
| CN102516612A (en) | Preparation method for porous starch/natural rubber compound | |
| CN108484288A (en) | Multiple trace element slow-release or control-release fertilizer | |
| CN108485207A (en) | A kind of degradable mulch and preparation method thereof with slow-release phosphate fertilizer | |
| CN110483930A (en) | Degradable EVA material and preparation method thereof, and application | |
| CN107141182A (en) | One preparation method for growing tobacco organic fertilizer special |
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 |