CN103788335A - Method for preparing polyurethane elastomer through solid-phase alcoholysis recovery of polyurethane - Google Patents
Method for preparing polyurethane elastomer through solid-phase alcoholysis recovery of polyurethane Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention discloses a method for preparing a polyurethane elastomer through the solid-phase alcoholysis recovery of polyurethane. The method comprises the following steps: carrying out alcoholysis reaction on 100 parts of leftover materials or scrap materials of the polyurethane, 0.5-100 parts of alcoholysis agent and 0.01-2 parts of catalyst in a strong mixer for 0.05-1.5h at the temperature of 160-220 DEG C and at the speed of 10-1,000r/min to obtain a solid alcoholysis product; uniformly mixing 100 parts of solid alcoholysis product, 30-40 parts of carbon black or white carbon black, 0-3 parts of dicumyl peroxide and 0-8 parts of isocyanate, and reacting for 3-15min at the temperature of 150-175 DEG C to obtain the polyurethane elastomer, wherein the tensile strength of the polyurethane elastomer is 8-26N/mm<2>, the breaking elongation is 150-500 percent, and the hardness is 65-96 Shore A. The method has the advantages of simple process, short period, complete recovery, low energy consumption and high product performance, and efficient and environment-friendly circulation of the polyurethane is realized.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of solid phase alcoholysis and reclaim the method that urethane is prepared polyurethane elastomer.
Background technology
Urethane (PU) material is widely used with its good physicals and good workability, accounts for 5% of world's macromolecular material ultimate production.Within 2010, global urethane consumption is broken through 1,870 ten thousand tons, and wherein Consumption of China amount is about 6,000,000 tons.Along with the fast development of polyurethane industrial, the scrap stock that thereupon produce and waste material are also more and more, comprising flexible PU foam, hard bubble, footwear material and spandex waste silk.Utilize not only land occupation, contaminate environment but also cause the poor efficiency utilization of organic carbon resource of the conventional process such as landfill and burning polyurethane waste material.Therefore urethane is recycled has become one of polyurethane industrial significant problem in the urgent need to address, and waste polyurethane is carried out to recycling, reduces environmental pollution, reduces the production cost of new product simultaneously, has realistic meaning.
The main method that urethane is recycled is at present chemical recycling, according to the difference of the kind of degradation agents and degradation condition, can be summarized as hydrolysis method, alkaline hydrolysis, amine-decomposing method, alcoholysis method, microwave assistant degradation method etc.The degradation production difference that the whole bag of tricks produces: hydrolysis method generates polyvalent alcohol and polyamine; Alkaline hydrolysis generates the carbonate of amine, alcohol and corresponding alkali; Amine-decomposing method generates polyvalent alcohol, amine, urea; Alcoholysis method generates polyol blends.[CN102432915A; CN101845152A; CN101445582A; CN201210059689] technology of main flow remains alcoholysis method in chemical recycling, be that urethane alcohol permutoid reaction occurs under the environment of dibasic alcohol is degraded, main regeneration obtains all kinds of polyether Glycols, aliphatic dihydric alcohol and part low molecular weight polyurethane dibasic alcohol, the method is widely used, and has realized industrialization in American-European countries.【US4159972；US6750260;US5556889;US5300530】
Urethane alcoholysis reaction technique at present, the common cycle is longer, and more than need at high temperature processing 7-8h, energy consumption also can correspondingly increase.This be because: 1) reaction in earlier stage need first the urethane predissolve after fragmentation in alcoholysis agent, and alcoholysis agent is generally the small molecule alcohol of 2-3 functionality, limited to the dissolved efficiency of urethane, cause this process slowly to be carried out; 2) initial viscosity of system is higher, makes urethane that the probability of alcohol permutoid reaction occur under the environment of alcoholysis agent not high, causes degradation speed slow; 3) conventional alcoholysis agent characteristic group is hydroxyl and ehter bond, and it, need separately add organic metal salt or tertiary amines organic catalyst and promote reaction without special promoter action the alcoholysis reaction of urethane.
Above-mentioned these methods are all to adopt liquid phase alcoholysis recovery process to obtain the polyol blends of liquid, and then as reclaimed materials for the preparation of the polyurethane products such as sizing agent or coating, there is the shortcomings such as complex manufacturing, the cycle is long, organic efficiency is low, energy consumption is large, product properties is low.
Summary of the invention
The method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis that the object of the invention is to propose in order to solve the technical problems such as in existing conventional polyurethanes liquid phase alcoholysis recovery process, reaction efficiency is low, the cycle is long, energy consumption is large.The method has that production technique is simple, the cycle is short, the polyurethane elastomer performance of less energy-consumption, final gained is high, thereby has realized efficient, the green circulatory utilization of urethane.
Technical scheme of the present invention
The method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis, be to add polyurethane waste material, alcoholysis agent, catalyzer in intensive mixer, under comparatively high temps and shear action, carry out alcoholysis, there is transesterification reaction, interrupt the cross-link bond of polyurethane waste material, the solid alcohol hydrolysis products obtaining directly can be used as the raw material of millable polyurethane elastomer, prepare polyurethane elastomer, specifically comprise the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 0.5-100 part: the ratio of 0.01-2 part is placed in intensive mixer, temperature is 180-220 ℃, under the condition that control rotating speed is 10-1000r/min, carry out alcoholysis reaction 0.05-1h, obtain solid alcohol hydrolysis products;
Described urethane scrap stock or waste material are one or more mixtures that form in flexible PU foam, polyurethane semihard foam, recovery polyurethane elastomer, spandex waste silk;
Described intensive mixer is Banbury mixer, twin screw extruder, multiple screw extruder, single screw extrusion machine, preferably Banbury mixer and twin screw extruder;
Described alcoholysis agent is molecular weight 62-100000, and hydroxy functionality is fatty alcohol, polyester polyol or the polyether glycol of 2-4;
Wherein said fatty alcohol is 62-100000, the fatty alcohol that hydroxy functionality is 2-4;
Described polyester polyol is 62-100000, and the polyester polyol that hydroxy functionality is 2-4 is preferably molecular weight 2000 polyester polyols;
Described polyether glycol is ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,6-ethylene glycol, 1,8-ethohexadiol, Hydrogenated Bisphenol A, glycol ether, dipropylene glycol, Triethylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, polyoxyethylene glycol, polypropylene glycol, take one or more polyether glycols that form as initiator such as glycerine, TriMethylolPropane(TMP), tetramethylolmethanes, be preferably the molecular weight that forms take polyoxyethylene glycol as the initiator polyether glycol as 6000;
Described catalyzer is organo-metallic salt catalyst, tertiary amines organic catalyst or calcium oxide;
Wherein said organo-metallic salt catalyst is dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin or dibutyltin diacetate, is preferably dibutyltin dilaurate or stannous octoate;
Described tertiary amines organic catalyst is triethylenediamine, N-methylmorpholine, dimethylaminopropylamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-sec.-propyl diethanolamine, N-normal-butyl diethanolamine, dipropanolamine, N-methyl dipropanolamine, N-ethyl dipropanolamine or N-sec.-propyl dipropanolamine, is preferably N-methylmorpholine, N-normal-butyl diethanolamine or dipropanolamine;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: carbon black or white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30-40 part: 0-3 part: the ratio of 0-8 part, in the solid alcohol hydrolysis products obtaining in step (1), add carbon black or white carbon black, dicumyl peroxide, isocyanic ester, after mixing, control temperature is 150-175 ℃ and carries out vulcanization reaction 3-15min, obtains polyurethane elastomer;
Described white carbon black is precipitated silica, and described carbon black is N330 carbon black or N550 carbon black;
Described isocyanic ester is diphenylmethanediisocyanate (hereinafter to be referred as MDI) or tolylene diisocyanate (hereinafter to be referred as TDI).
The method that urethane is prepared polyurethane elastomer is reclaimed in above-mentioned solid phase alcoholysis, and the tensile strength of the polyurethane elastomer of final gained can reach 8-26N/mm
2, elongation at break can reach 150-500%, and hardness can reach Shao 65-96(A)
Useful technique effect of the present invention
The method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis of the present invention; because the present invention has adopted intensive mixer; therefore in preparation process, need not add solvent and nitrogen protection; abandon the shortcomings such as traditional alcoholysis high energy consumption, organic efficiency are low, complex process, there is the advantages such as environmental protection and energy saving.
Further, the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis of the present invention, because raw material used is urethane scrap stock or waste material, therefore can realize efficient, the green circulatory utilization of urethane, urethane scrap stock or waste recovery rate can reach 100%.
Further, the polyurethane elastomer that urethane is prepared the method gained of polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis of the present invention, and its tensile strength can reach 8-26N/mm
2, elongation at break can reach 150-500%, hardness can reach Shao 65-96(A), approach the performance of mixing polyether types of polyurethane rubber, there is good application prospect.
Embodiment
Below by embodiment, the present invention is further elaborated, but do not limit the present invention.
In the embodiment of the present invention, according to tensile strength, the elongation at break of GBT 528-2009 standard test urethanes, measure the hardness of urethane according to GBT 23651-2009;
Measure Akron abrasion according to GB-T1689-1998;
Measure curing time according to GB/T 16584-1996.
The stretching strength determination universal testing machine used of urethane adopts SUN500, CARDANOAL CAMPO (VA)-ITALIA.
In various embodiments of the present invention, the model of equipment used and the information of manufacturer are as follows:
Single screw extrusion machine, model: CSS-273 type, Changchun Inst of Testing Machine produces;
Wear testing machine, model: JC-1076, Jiangdu absolute sincerity testing tool factory produces;
Banbury mixer, model: S (X) M-1L-KA type, Changzhou Su Yuan rubber and plastic Science and Technology Ltd. produces;
Twin screw extruder, in the same way, Nanjing Ke Ya company produces model: TE-35.
embodiment 1
The method that urethane is prepared polyurethane elastomer is reclaimed in solid phase alcoholysis, specifically comprises the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 6 parts: the ratio of 0.02 part is placed in intensive mixer, temperature is 200 ℃, under the condition that control rotating speed is 30r/min, carry out alcoholysis reaction 0.5h, obtain solid alcohol hydrolysis products;
Described urethane scrap stock or waste material are spandex waste silk;
Described intensive mixer adopts Banbury mixer;
Described alcoholysis agent is the polyoxyethylene glycol that molecular weight is 100000, hydroxy functionality is 2;
Described catalyzer is calcium oxide;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 2 parts: the ratio of 8 parts, in the solid alcohol hydrolysis products obtaining in step (1), add white carbon black, dicumyl peroxide, isocyanic ester, after mixing, control temperature is 150 ℃ and carries out vulcanization reaction 15min, obtains polyurethane elastomer;
Described white carbon black is precipitated silica;
Described isocyanic ester is MDI.
The polyurethane elastomer performance of above-mentioned gained after measured, its tensile strength 26N/mm
2, elongation at break 150%, hardness (Shao A) 96, Akron abrasion 0.03cm
3/ 1.61km.
embodiment 2
The method that urethane is prepared polyurethane elastomer is reclaimed in solid phase alcoholysis, specifically comprises the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 50 parts: the ratio of 0.02 part is placed in intensive mixer, temperature is 180 ℃, under the condition that control rotating speed is 100r/min, carry out alcoholysis reaction 0.05h, obtain solid alcohol hydrolysis products;
Described urethane scrap stock or waste material are flexible PU foam (memory foam);
Described intensive mixer adopts twin screw extruder.
Described alcoholysis agent is BDO;
Described catalyzer is dibutyltin dilaurate;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 0 part: the ratio of 5 parts, in the solid alcohol hydrolysis products obtaining in step (1), add carbon black, isocyanic ester, after mixing, control temperature is 150 ℃ and carries out vulcanization reaction 15min, obtains polyurethane elastomer;
Described carbon black is N330 carbon black;
Described isocyanic ester is MDI.
The polyurethane elastomer performance of above-mentioned gained after measured, its tensile strength 8N/mm
2, elongation at break 500%, hardness (Shao A) 65, Akron abrasion 0.25cm
3/ 1.61km.
embodiment 3
The method that urethane is prepared polyurethane elastomer is reclaimed in solid phase alcoholysis, specifically comprises the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 100 parts: the ratio of 2 parts is placed in intensive mixer, temperature is 220 ℃, controlling rotating speed is to carry out alcoholysis reaction 0.5h under the condition of 30 r/min, obtains solid alcohol hydrolysis products.
Described urethane scrap stock or waste material are polyurethane semihard foam;
Described intensive mixer adopts Banbury mixer;
Described alcoholysis agent is the polyester polyol that molecular weight is 2000, hydroxy functionality is 2;
Described catalyzer is N-normal-butyl diethanolamine;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 2 parts: the ratio of 0 part, in the solid alcohol hydrolysis products obtaining in step (1), add white carbon black, dicumyl peroxide, after mixing, control temperature is 175 ℃ and carries out vulcanization reaction 3min, obtains polyurethane elastomer;
Described white carbon black is precipitated silica.
The polyurethane elastomer performance of above-mentioned gained after measured, its tensile strength 9N/mm
2, elongation at break 300%, hardness (Shao A) 70, Akron abrasion 0.18cm
3/ 1.61km.
embodiment 4
The method that urethane is prepared polyurethane elastomer is reclaimed in solid phase alcoholysis, specifically comprises the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 0.5 part: the ratio of 0.01 part is placed in intensive mixer, temperature is 200 ℃, under the condition that control rotating speed is 10r/min, carry out alcoholysis reaction 0.1h, obtain solid alcohol hydrolysis products;
Described urethane scrap stock or waste material are for reclaiming polyurethane elastomer;
Described intensive mixer adopts single screw extrusion machine;
Described alcoholysis agent is tetramethylolmethane;
Described catalyzer is N-methylmorpholine;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 3 parts: the ratio of 2 parts, in the solid alcohol hydrolysis products obtaining in step (1), add white carbon black, dicumyl peroxide, isocyanic ester, after mixing, control temperature is 160 ℃ and carries out vulcanization reaction 10min, obtains polyurethane elastomer;
Described white carbon black is precipitated silica;
Described isocyanic ester is TDI.
The polyurethane elastomer performance of above-mentioned gained after measured, its tensile strength 25N/mm
2, elongation at break 350%, hardness (Shao A) 85, Akron abrasion 0.08cm
3/ 1.61km.
embodiment 5
The method that urethane is prepared polyurethane elastomer is reclaimed in solid phase alcoholysis, specifically comprises the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 6 parts: the ratio of 0.05 part is placed in intensive mixer, temperature is 200 ℃, under the condition that control rotating speed is 40r/min, carry out alcoholysis reaction 1h, obtain solid alcohol hydrolysis products;
Described urethane scrap stock or waste material are that recovery polyurethane elastomer and spandex waste silk are the mixture of 1:1 composition by weight calculating;
Described intensive mixer is Banbury mixer;
Described alcoholysis agent is propylene glycol;
Described catalyzer is dipropanolamine;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 2 parts: the ratio of 5 parts, in the solid alcohol hydrolysis products obtaining in step (1), add carbon black, dicumyl peroxide, isocyanic ester, after mixing, control temperature is 160 ℃ and carries out vulcanization reaction 10min, obtains polyurethane elastomer;
Described carbon black is N550 carbon black;
Described isocyanic ester is TDI.
The polyurethane elastomer performance of above-mentioned gained after measured, its tensile strength 18N/mm
2, elongation at break 380%, hardness (Shao A) 90, Akron abrasion 0.05cm
3/ 1.61km.
embodiment 6
The method that urethane is prepared polyurethane elastomer is reclaimed in solid phase alcoholysis, specifically comprises the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 20 parts: the ratio of 0.1 part is placed in intensive mixer, temperature is 190 ℃, under the condition that control rotating speed is 50r/min, carry out alcoholysis reaction 1h, obtain solid alcohol hydrolysis products.
Described urethane scrap stock or waste material are the mixture that flexible PU foam and spandex waste silk form for 1:1 by weight calculating;
Described intensive mixer is Banbury mixer;
The described alcoholysis agent molecular weight that to be polyoxyethylene glycol take molecular weight as 600 form as initiator as 6000, the polyether glycol of hydroxy functionality as 3;
Described catalyzer is stannous octoate;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 40 parts: 3 parts: the ratio of 8 parts, in the solid alcohol hydrolysis products obtaining in step (1), add carbon black, dicumyl peroxide, isocyanic ester, after mixing, control temperature is 160 ℃ and carries out vulcanization reaction 10min, obtains polyurethane elastomer;
Described carbon black is N550 carbon black;
Described isocyanic ester is TDI.
The polyurethane elastomer performance of above-mentioned gained after measured, its tensile strength 15N/mm
2, elongation at break 350%, hardness (Shao A) 88, Akron abrasion 0.07cm
3/ 1.61km.
comparative example 1
The method that urethane is prepared polyurethane elastomer is reclaimed in liquid phase alcoholysis, specifically comprises the steps:
Agitator is being housed, condenser, in three mouthfuls of round-bottomed flasks of thermometer by urethane scrap stock or waste material and alcoholysis agent, catalyzer is by weight calculating, be urethane scrap stock or waste material: solvent: alcoholysis agent: catalyzer is 100 parts: 0 part: 75 parts: 0.8 part jointly mix after, under nitrogen protection, be warming up to 160 ℃, predissolve 60min, then controlling rotating speed and be 100r/min carries out for the first time after alcoholysis reaction 6.5h, be warming up to again 180 ℃ and carry out alcoholysis reaction 0.5h for the second time, discharging after being cooled to 80 ℃ after alcoholysis reaction for the second time, obtain dark-brown alcoholysis product, the rate of recovery of urethane is 92%,
Described urethane scrap stock or waste material are that 100.0g controls the flexible PU foam scrap stock that globule size is 5mm after crusher in crushing;
Described alcoholysis agent is the polyoxyethylene glycol of molecular weight 400;
Described catalyzer is stannous octoate.
By above-mentioned obtained dark-brown alcoholysis product and isocyanic ester by and chainextender 1; 4 butyleneglycols are 1:1 according to isocyano and hydroxyl mol ratio; base polyurethane prepolymer for use as is prepared in 110 ℃ of nitrogen protections; be cooled to 70 ℃ of warps and supplement chainextender, reaction 30min, 73 ℃ of steady temperatures; add again 0.1%(weight ratio) stannous octoate catalyst; question response thing starts retrogradation, pours into rapidly in tetrafluoroethylene mould, removes volatile matter obtain urethane virgin rubber through 110 ℃ of 24h forced air dryings.
By in 100 parts of urethane virgin rubbers of above-mentioned gained, add 30 parts of precipitated silicas, after 2 parts of dicumyl peroxides and 3 parts of isocyanic ester (TDI dimer) mix, carry out vulcanization reaction 15min through 160 ℃, obtain polyurethane elastomer.
The polyurethane elastomer performance of above-mentioned gained after measured, its tensile strength 8N/mm
2, elongation at break 330%, hardness (Shao A) 72, Akron abrasion 0.24cm
3/ 1.61km.
The above embodiments 1～6 and comparative example 1 are prepared to time that alcoholysis product consumes, utilize polyurethane elastomer performance prepared by alcoholysis product to be listed as follows:
From table 1, embodiment 1-6 and comparative example's 1 result can be found out, embodiment 1-6 adopts solid phase alcoholysis recovery urethane scrap stock or waste material to prepare the method for polyurethane elastomer, the time consuming is short, utilizing solid alcohol hydrolysis products to prepare cross-linked rubber is greatly to shorten the time that polyurethane elastomer consumes, and the cross-linked rubber of preparation is polyurethane possesses excellent properties.And contrast implements 1, what adopt is liquid phase alcoholysis process, what finally obtain is liquid phase polyvalent alcohol and amine substance, by all degradeds of long molecule segment and chemically crosslinked point in reclaimed materials, thereby the needed time is long, and final gained is the mixture of liquid polyol and amine, and its performance is greatly deteriorated.Show thus, employing solid phase alcoholysis recovery urethane scrap stock of the present invention or waste material are prepared the method for polyurethane elastomer, not only keep long chain molecule structure in urethane scrap stock or waste material, and by crosslinking structure controlled degradation, the alcoholysis time is short, and the cross-linked rubber of final gained is polyurethane possesses excellent properties.
Further; solid phase alcoholysis recovery urethane scrap stock of the present invention or waste material are prepared the method for polyurethane elastomer; solid phase alcoholysis adopts high intensity mixer; in alcoholysis process, completely cut off air; without nitrogen protection; therefore recovery process is simple, has abandoned the defect that needs nitrogen protection at present conventional liquid phase alcoholysis process.Further, solid phase alcoholysis process waste material 100% of the present invention reclaims, and traditional technology can only be partially recycled, thereby has greatly reduced the secondary pollution to environment, possesses the feature of energy-conserving and environment-protective.
In sum; the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid-state alcoholysis of the present invention; owing to having abandoned traditional interpolation solvent or microwave degradation to techniques such as liquid polyols; adopt controlled degradation directly to obtain solid-state urethane, then after sulfuration, obtain high performance elastomer, the reaction times is short; technique is simple; all environmental protection is reclaimed, and has very big innovation, has good application prospect.
Above said content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (7)
1. the method that urethane is prepared polyurethane elastomer is reclaimed in solid phase alcoholysis, it is characterized in that specifically comprising the steps:
(1), by urethane scrap stock or waste material and alcoholysis agent, catalyzer by weight calculating, be urethane scrap stock or waste material: alcoholysis agent: catalyzer is 100 parts: 0.5-100 part: the ratio of 0.01-2 part is placed in intensive mixer, control temperature is 180-220 ℃, rotating speed is to carry out alcoholysis reaction 0.05-1h under the condition of 10-1000r/min, obtains solid alcohol hydrolysis products;
Described urethane scrap stock or waste material are one or more mixtures that form in flexible PU foam, polyurethane semihard foam, polyurethane elastomer, spandex waste silk;
Described alcoholysis agent is fatty alcohol, polyester polyol or polyether glycol;
Wherein said fatty alcohol is that molecular weight is the fatty alcohol that 62-100000, hydroxy functionality are 2-4;
Described polyester polyol is that molecular weight is the polyester polyol that 62-100000, hydroxy functionality are 2-4;
Described polyether glycol is ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,6-ethylene glycol, 1,8-ethohexadiol, Hydrogenated Bisphenol A, glycol ether, dipropylene glycol, Triethylene glycol, glycerine, TriMethylolPropane(TMP), tetramethylolmethane, polyoxyethylene glycol, polypropylene glycol, take one or more molecular weight that form as initiator in glycerine, TriMethylolPropane(TMP), tetramethylolmethane as 62-100000, hydroxy functionality is the polyether glycol of 2-4;
Described catalyzer is organo-metallic salt catalyst, tertiary amines organic catalyst or calcium oxide;
Wherein said organo-metallic salt catalyst is dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin or dibutyltin diacetate;
Described tertiary amines organic catalyst is triethylenediamine, N-methylmorpholine, dimethylaminopropylamine, trolamine, N methyldiethanol amine, N-ethyldiethanolamine, N-sec.-propyl diethanolamine, N-normal-butyl diethanolamine, dipropanolamine, N-methyl dipropanolamine, N-ethyl dipropanolamine or N-sec.-propyl dipropanolamine;
(2), calculate by weight, be the solid alcohol hydrolysis products that step (1) obtains: carbon black or white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30-40 part: 0-3 part: the ratio of 0-8 part, in the solid alcohol hydrolysis products obtaining in step (1), add carbon black or white carbon black, dicumyl peroxide, isocyanic ester, after mixing, control temperature is 150-175 ℃ and carries out vulcanization reaction 3-15min, obtains polyurethane elastomer;
Described white carbon black is precipitated silica, and described carbon black is N330 carbon black or N550 carbon black;
Described isocyanic ester is diphenylmethanediisocyanate or tolylene diisocyanate.
2. the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis as claimed in claim 1, it is characterized in that urethane scrap stock or the waste material described in step (1): alcoholysis agent: catalyzer is 100 parts: 6 parts: 0.02 part, temperature is 200 ℃, under the condition that control rotating speed is 30r/min, carries out alcoholysis reaction 0.5h;
Described urethane scrap stock or waste material are spandex waste silk;
Described alcoholysis agent is the polyoxyethylene glycol that molecular weight is 100000, hydroxy functionality is 2;
Described catalyzer is calcium oxide;
Solid alcohol hydrolysis products described in step (2): white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 2 parts: 8 parts, control temperature is 150 ℃ and carries out vulcanization reaction 15min;
Described white carbon black is precipitated silica;
Described isocyanic ester is diphenylmethanediisocyanate.
3. the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis as claimed in claim 1, it is characterized in that urethane scrap stock or the waste material described in step (1): alcoholysis agent: catalyzer is 100 parts: 50 parts: 0.02 part, temperature is 180 ℃, under the condition that control rotating speed is 100r/min, carries out alcoholysis reaction 0.05h;
Described urethane scrap stock or waste material are flexible PU foam;
Described intensive mixer adopts twin screw extruder; Described alcoholysis agent is BDO;
Described catalyzer is dibutyltin dilaurate;
Solid alcohol hydrolysis products described in step (2): carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 0 part: 5 parts, in the solid alcohol hydrolysis products obtaining in step (1), add carbon black, isocyanic ester, after mixing, control temperature is 150 ℃ and carries out vulcanization reaction 15min;
Described carbon black is N330 carbon black;
Described isocyanic ester is diphenylmethanediisocyanate.
4. the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis as claimed in claim 1, it is characterized in that urethane scrap stock or the waste material described in step (1): alcoholysis agent: catalyzer is 100 parts: 100 parts: 2 parts, temperature is 220 ℃, and controlling rotating speed is to carry out alcoholysis reaction 0.5h under the condition of 30 r/min;
Described urethane scrap stock or waste material are polyurethane semihard foam;
Described intensive mixer adopts Banbury mixer;
Described alcoholysis agent is that molecular weight is 2000, the polyester polyol that hydroxy functionality is 2;
Described catalyzer is N-normal-butyl diethanolamine;
Solid alcohol hydrolysis products described in step (2): white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 2 parts: 0 part, control temperature is 175 ℃ and carries out vulcanization reaction 3min;
Described white carbon black is precipitated silica.
5. the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis as claimed in claim 1, it is characterized in that urethane scrap stock or the waste material described in step (1): alcoholysis agent: catalyzer is 100 parts: 0.5 part: 0.01 part, temperature is 200 ℃, under the condition that control rotating speed is 10r/min, carries out alcoholysis reaction 0.1h;
Described urethane scrap stock or waste material are for reclaiming polyurethane elastomer;
Described intensive mixer adopts single screw extrusion machine;
Described alcoholysis agent is tetramethylolmethane;
Described catalyzer is N-methylmorpholine;
Solid alcohol hydrolysis products described in step (2): white carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 3 parts: 2 parts, control temperature is 160 ℃ and carries out vulcanization reaction 10min;
Described white carbon black is precipitated silica;
Described isocyanic ester is tolylene diisocyanate.
6. the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis as claimed in claim 1, it is characterized in that urethane scrap stock or the waste material described in step (1): alcoholysis agent: catalyzer is 100 parts: 6 parts: 0.05 part, temperature is 200 ℃, under the condition that control rotating speed is 40r/min, carries out alcoholysis reaction 1h;
Described urethane scrap stock or waste material are that recovery polyurethane elastomer and spandex waste silk are the mixture of 1:1 composition by weight calculating;
Described intensive mixer is Banbury mixer;
Described alcoholysis agent is propylene glycol;
Described catalyzer is dipropanolamine;
Solid alcohol hydrolysis products described in step (2): carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 30 parts: 2 parts: 5 parts, control temperature is 160 ℃ and carries out vulcanization reaction 10min
Described carbon black is N550 carbon black;
Described isocyanic ester is tolylene diisocyanate.
7. the method that urethane is prepared polyurethane elastomer is reclaimed in a kind of solid phase alcoholysis as claimed in claim 1, it is characterized in that urethane scrap stock or the waste material described in step (1): alcoholysis agent: catalyzer is 100 parts: 20 parts: 0.1 part, temperature is 190 ℃, under the condition that control rotating speed is 50r/min, carries out alcoholysis reaction 1h;
Described urethane scrap stock or waste material are the mixture that flexible PU foam and spandex waste silk form for 1:1 by weight calculating;
Described intensive mixer is Banbury mixer;
The described alcoholysis agent molecular weight that to be polyoxyethylene glycol take molecular weight as 600 form as initiator as 6000, the polyether glycol of hydroxy functionality as 3;
Described catalyzer is stannous octoate;
Solid alcohol hydrolysis products described in step (2): carbon black: dicumyl peroxide: isocyanic ester is 100 parts: 40 parts: 3 parts: 8 parts, control temperature is 160 ℃ and carries out vulcanization reaction 10min;
Described carbon black is N550 carbon black;
Described isocyanic ester is tolylene diisocyanate.
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| CN104073904A (en) * | 2014-07-17 | 2014-10-01 | 江苏侨新纤维有限公司 | Method for preparing coarse denier spandex fiber for hygienic material by adopting spandex silk waste |
| CN105860000A (en) * | 2016-04-12 | 2016-08-17 | 广州聚天化工科技有限公司 | Waterproof coating prepolymer prepared based on polyurethane degradation product, and preparation method and application thereof |
| CN106750510A (en) * | 2017-01-13 | 2017-05-31 | 郑州中远氨纶工程技术有限公司 | The processing method and polyurethane elastomer of urethane oligomer waste liquid |
| CN110527136A (en) * | 2019-09-12 | 2019-12-03 | 长春工业大学 | The method of waste and old hard polyurethane material hydro-thermal catalytic degradation preparation polyether polyol |
| CN113699618A (en) * | 2021-08-26 | 2021-11-26 | 诸暨华海氨纶有限公司 | Method for preparing high-resilience spandex fiber by utilizing spandex waste silk |
| CN113999429A (en) * | 2021-12-21 | 2022-02-01 | 浙江工业大学 | Method for efficiently degrading polyurethane coating solid waste |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104073904A (en) * | 2014-07-17 | 2014-10-01 | 江苏侨新纤维有限公司 | Method for preparing coarse denier spandex fiber for hygienic material by adopting spandex silk waste |
| CN104073904B (en) * | 2014-07-17 | 2016-01-20 | 江苏侨新纤维有限公司 | A kind of spandex waste silk that utilizes prepares the method for hygienic material with thick dawn spandex fibre |
| CN105860000A (en) * | 2016-04-12 | 2016-08-17 | 广州聚天化工科技有限公司 | Waterproof coating prepolymer prepared based on polyurethane degradation product, and preparation method and application thereof |
| CN105860000B (en) * | 2016-04-12 | 2019-03-26 | 广州聚天化工科技有限公司 | A kind of water-repellent paint performed polymer and its preparation method and application based on polyurethane degraded product preparation |
| CN106750510A (en) * | 2017-01-13 | 2017-05-31 | 郑州中远氨纶工程技术有限公司 | The processing method and polyurethane elastomer of urethane oligomer waste liquid |
| CN106750510B (en) * | 2017-01-13 | 2020-04-03 | 郑州中远氨纶工程技术有限公司 | Method for treating polyurethane oligomer waste liquid and polyurethane elastomer |
| CN110527136A (en) * | 2019-09-12 | 2019-12-03 | 长春工业大学 | The method of waste and old hard polyurethane material hydro-thermal catalytic degradation preparation polyether polyol |
| CN113699618A (en) * | 2021-08-26 | 2021-11-26 | 诸暨华海氨纶有限公司 | Method for preparing high-resilience spandex fiber by utilizing spandex waste silk |
| CN113699618B (en) * | 2021-08-26 | 2022-04-15 | 诸暨华海氨纶有限公司 | Method for preparing high-resilience spandex fiber by utilizing spandex waste silk |
| CN113999429A (en) * | 2021-12-21 | 2022-02-01 | 浙江工业大学 | Method for efficiently degrading polyurethane coating solid waste |
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