CN103146337B - Method for preparing single-component wet cured polyurethane hot melt adhesive by utilizing spandex waste wires - Google Patents
Method for preparing single-component wet cured polyurethane hot melt adhesive by utilizing spandex waste wires Download PDFInfo
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- CN103146337B CN103146337B CN201310091008.9A CN201310091008A CN103146337B CN 103146337 B CN103146337 B CN 103146337B CN 201310091008 A CN201310091008 A CN 201310091008A CN 103146337 B CN103146337 B CN 103146337B
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Abstract
The invention discloses a method for preparing a single-component wet cured polyurethane hot melt adhesive by utilizing spandex waste wires. The method comprises the spandex waste wire degradation process and the polyurethane hot melt adhesive synthesis process. According to the method, the defects that the conventional polyurethane hot melt adhesive is extremely high in production cost and raw material price and the spandex waste wires are not fully utilized are overcome, and by employing the method, the degradation products are not required to be separated and are directly used, the production cost of the polyurethane hot melt adhesive is greatly reduced, and lots of spandex waste wires can be recycled. According to the prepared polyurethane hot melt adhesive, high economic benefits and social benefits can be obtained.
Description
Technical field
The invention belongs to the method and technology field of spandex waste silk recycling, specifically belong to the method for utilizing spandex waste silk to prepare the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives.
Background technology
Polyurethane elastomeric fiber claims again spandex, English Polyurethane fiber(PU fiber by name), be a kind ofly by polyurethane ester group content, to be greater than 85% and have the artificial man-made fiber that the segmented copolymer of linear segmented structure is formed by weaving, the hard segment that the soft chain segment that this segmented copolymer is mainly comprised of low-molecular-weight polyester or polyethers and aromatic diisocyanate form reacts synthetic under certain condition.Along with polyurethane fiber rolling up in China's production and usage quantity, inevitably can produce a large amount of polyurethane fiber waste materials, it is spandex waste silk, most of polyurethane fibers belong to thermosetting material, have insoluble not molten characteristic, this just brings very large difficulty to the re-using of polyurethane waste material.At present, the recycling approach of polyurethane waste material mainly contains: energy method, Physical and chemical method; At present main employing burned, as the method for packing filler or chemical degradation, processed, and burns or low as the method resource utilization of packing filler, also brings new pollution, and chemical degradation complex process, cost be higher, be difficult to promote.Along with the raising of people's environmental consciousness, realize low pollution, lasting making rational use of resources, become the problem that people must overcome and consider in actual production.The polyurethane fiber total quantity consumed of China in 2007 accounts for 28.5% of global total quantity consumed, is only second to North America, it is predicted that 2012 ~ 2015 years China will become the main consumption market of global polyurethane fiber.Therefore, the recycling of polyurethane fiber waste material has been to need the problem of solution emphatically.
And on the other hand, reactive polyurethane hot melt is equipped with corresponding auxiliary agent by the base polyurethane prepolymer for use as of single component, solvent-free isocyanate terminated base and is prepared from.Its main component is by the synthetic isocyanate groups terminated polyurethane prepolymers of polyester polyol, polyether glycol and vulcabond, after melting applying glue, can meet moisture fast setting, has just glutinous intensity preferably; In after fixing process, moisture diffusion enters sizing agent, react and form urea, biuret and allophanate with the isocyanic ester of prepolymer end group, make the low molecule of linear prepolymer form crosslinked macromolecular structure, thereby there is better high temperature resistant, resistance to solvent and water resistance than traditional hot melt adhesive.At present, One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is widely used in vehicle structure and component, as windshield glass sealing and lamp assembled etc.; Textile industry and shoe industry, as bonding in fabric seam and sole is bonding; Books unsewn binding; Wood working and furniture industry; Building trade.In a word, at needs, locate fast, bonded part needs the occasion of resistance to high humidity, comparatively high temps and higher ambient pressure all can adopt moisture-curable polyurethane hot melt adhesive.So just caused moisture-curable polyurethane hot melt adhesive to obtain more and more widely application, it is too high that preparation method's ubiquity of present moisture-curable polyurethane hot melt adhesive production cost, range of application little problem.
Summary of the invention
The invention provides a kind of method of utilizing spandex waste silk to prepare the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, comprise the degradation process of spandex waste silk and the building-up process of adhesive for polyurethane, the method has overcome current polyurethane hot melt production cost and the prices of raw and semifnished materials are high, spandex waste silk is underused defect, adopting said method, degraded product need not be separated and directly use, and the production cost that greatly reduces polyurethane hot melt can also be recycled a large amount of spandex waste silks.Economic benefit and social benefit that the adhesive for polyurethane of preparation can obtain.
For achieving the above object, technical scheme of the present invention is:
Utilize spandex waste silk to prepare a method for the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, step is as follows:
Step 1: pretreatment stage, be about to spandex waste silk and through fiber pulverizer, be ground into the spandex waste silk of desired length, the spandex waste silk of desired length is just spandex waste silk to be added like this;
Step 2: DeR stage, the raw material using in stage in this DeR is alcoholysis agent, catalyzer and the spandex waste silk to be added that obtains in step 1 for DeR, first in the three-necked bottle of agitator and prolong is housed, first according to default alcoholysis agent, in the parts by weight ratio range dealing three-necked bottle with spandex waste silk to be added, add alcoholysis agent, subsequently the alcoholysis agent in three-necked bottle is carried out to heat temperature raising, heat temperature raising is until temperature is 180-200 ℃, then 1/10 the spandex waste silk that part by weight is accounted for to spandex waste silk to be added adds in three-necked bottle, follow according to default DeR the parts by weight ratio range with the raw material using in the shared DeR of the catalyzer stage, in three-necked bottle, add DeR catalyzer, then with agitator, the raw material adding in three-necked bottle is carried out to the DeR under constant temperature stirring, in DeR process, in three-necked bottle, add remaining spandex waste silk to be added in batches, the reaction solution viscosity that is accompanied by the dissolving of spandex waste silk like this when DeR and carries out DeR in three-necked bottle also increases, according to the increase of reaction solution viscosity, by default speed, accelerate stirring reaction, when the reaction solution hydroxyl value that stirring reaction forms through DeR after four hours and in three-necked bottle is stabilized in default scope, stop stirring reaction, after the reaction solution in three-necked bottle is cooled to temperature range to be 95 ℃-105 ℃, with 100 ~ 120 object filtering nets, the reaction solution in three-necked bottle is carried out to filtered while hot, reaction solution after filtered while hot is cooled to the yellow thick liquid obtaining after normal temperature, be spandex waste silk degraded product dibasic alcohol, this DeR product is sealed and saved backup,
Step 3: the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, the raw material using at the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is vulcabond, moisture curing catalysts, oxidation inhibitor, viscosity stabilizer, the spandex waste silk degraded product dibasic alcohol and the polyester polyol that in step 2, obtain, polyether glycol, be about to polyester polyol, polyether glycol joins and in flask, forms mixture by the parts by weight ratio range of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives with the spandex waste silk degraded product dibasic alcohol obtaining in step 2, after this mixture is stirred with agitator, after mixture in this flask is warming up to temperature range and is 120-130 ℃, then this mixture is carried out to vacuum hydro-extraction 2-3 hour, then the mixture after vacuum hydro-extraction being cooled to temperature range is 70 ℃-80 ℃, in flask, pass into nitrogen protection, by the parts by weight scope of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, in the mixture after vacuum hydro-extraction, add vulcabond simultaneously, and to having added the mixture of vulcabond to stir according to default speed with agitator, in whipping process, carry out the building-up reactions of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, after the lasting 2h of stirring, obtain the Primary product of building-up reactions, parts by weight ratio range by the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives adds moisture curing catalysts, oxidation inhibitor involutoryly becomes the Primary product of reaction to carry out obtaining the glutinous agent of synthetic One-Component Moisture-Curable Polyurethane Hot Melt Adhesives after building-up reactions 20min with continuing after viscosity stabilizer, the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is poured out from flask and pack in the bottle of sealing standby.
Alcoholysis agent in described step 2 is the polyvalent alcohol of 2-10 carbon atom, the polyvalent alcohol that the alcoholysis agent used of described DeR is 2-10 carbon atom, the polyvalent alcohol of 2-10 carbon atom comprises ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, glycol ether, Triethylene glycol, tetraethylene-glycol, glycerol, low-molecular-weight polyethers or polyester polyol.
Described DeR used catalyst is zinc acetate, tin tetrachloride, stannous octoate, triethylamine or dibutyl tin laurate, also can adopt tin tetrachloride, stannous octoate, triethylamine, dibutyl tin laurate etc. to be combined with each other and to form DeR used catalyst according to default ratio.
The parts by weight proportioning of the raw material that the DeR of described step 2 used in the stage is: 16-33 part small molecules polyvalent alcohol, 33-80 part spandex waste silk and 0.2-0.5 part DeR catalyzer.
Polyvalent alcohol in described step 3 in the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is polyester polyol and polyether glycol, and the molecular weight of polyester polyol and polyether glycol is in 1000～5000 scopes.
Described vulcabond comprises aromatic series, aliphatics and alicyclic diisocyanate, mainly be not limited to tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), the mixture of one or more in isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI).
Described moisture curing catalysts is one or more the composite use in organic tin, organo-bismuth class or amine.
The parts by weight proportioning of the raw material that in described step 3, the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives uses is: 20-28 part spandex waste silk part degraded product dibasic alcohol, 18-34 part polyester polyol, 5-12 part high crystalline polyvalent alcohol, 30 ~ 45 parts of vulcabond, 0.1 ~ 0.15 part of moisture curing catalysts catalyzer, 0.1 ~ 0.15 portion of viscosity stabilizer and 0.1 ~ 0.5 part of oxidation inhibitor.
Method advantage of the present invention has overcome current polyurethane hot melt production cost and the prices of raw and semifnished materials are high, spandex waste silk is underused defect, adopting said method, degraded product need not be separated and directly use, and the production cost that greatly reduces polyurethane hot melt can also be recycled a large amount of spandex waste silks.Economic benefit and social benefit that the adhesive for polyurethane of preparation can obtain.
Embodiment
Below by concrete embodiment, the present invention will be further described:
Embodiment 1
Utilize spandex waste silk to prepare the method for the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, step is as follows:
Step 1: pretreatment stage, be about to spandex waste silk and through fiber pulverizer, be ground into the spandex waste silk of desired length, the spandex waste silk of desired length is just spandex waste silk to be added like this;
Step 2: DeR stage, the raw material using in stage in this DeR is alcoholysis agent, catalyzer and the spandex waste silk to be added that obtains in step 1 for DeR, first in the three-necked bottle of agitator and prolong is housed, first according to default alcoholysis agent, in the parts by weight ratio range dealing three-necked bottle with spandex waste silk to be added, add alcoholysis agent, this alcoholysis agent is glycol ether, subsequently the alcoholysis agent in three-necked bottle is carried out to heat temperature raising, heat temperature raising is until temperature is 180 ℃, again in spandex waste silk to be added, 1/10 the spandex waste silk that part by weight is accounted for to spandex waste silk to be added adds in three-necked bottle, follow according to default DeR the parts by weight ratio range with the raw material using in the shared DeR of the catalyzer stage, in three-necked bottle, add DeR catalyzer, described DeR catalyzer is tin tetrachloride, then with agitator, the raw material adding in three-necked bottle is carried out to the DeR under constant temperature stirring, in DeR process, in three-necked bottle, add remaining spandex waste silk to be added in batches, the reaction solution viscosity that is accompanied by the dissolving of spandex waste silk like this when DeR and carries out DeR in three-necked bottle also increases, according to the increase of reaction solution viscosity, by default speed, accelerate stirring reaction, when the reaction solution hydroxyl value that stirring reaction forms through DeR after four hours and in three-necked bottle is stabilized in default scope, stop stirring reaction, after the reaction solution in three-necked bottle is cooled to temperature to be 100 ℃, with 120 object filtering nets, the reaction solution in three-necked bottle is carried out to filtered while hot, reaction solution after filtered while hot is cooled to the yellow thick liquid obtaining after normal temperature, be spandex waste silk degraded product dibasic alcohol, this DeR product is sealed and saved backup,
Step 3: the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, the raw material using at the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is vulcabond, moisture curing catalysts, oxidation inhibitor, viscosity stabilizer, the spandex waste silk degraded product dibasic alcohol and the polyester polyol that in step 2, obtain, polyether glycol, be about to polyester polyol, polyether glycol joins and in flask, forms mixture by the parts by weight ratio range of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives with the spandex waste silk degraded product dibasic alcohol obtaining in step 2, polyester polyol is that polyester polyol CMA-44 and poly-hexanodioic acid 1.4-butanediol ester glycol are mixed to form, after this mixture is stirred with agitator, after mixture in this flask is warming up to temperature and is 120 ℃, then this mixture is carried out to vacuum hydro-extraction 2 hours, then the mixture after vacuum hydro-extraction being cooled to temperature is 80 ℃, in flask, pass into nitrogen protection, by the parts by weight scope of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, in the mixture after vacuum hydro-extraction, add vulcabond simultaneously, this vulcabond is diphenylmethane isocyanate, and to having added the mixture of vulcabond to stir according to default speed with agitator, in whipping process, carry out the building-up reactions of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, after the lasting 2h of stirring, obtain the Primary product of building-up reactions, parts by weight ratio range by the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives adds moisture curing catalysts, oxidation inhibitor involutoryly becomes the Primary product of reaction to carry out obtaining the glutinous agent of synthetic One-Component Moisture-Curable Polyurethane Hot Melt Adhesives after building-up reactions 20min with continuing after viscosity stabilizer, this moisture curing catalysts is dibutyl tin laurate, the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is poured out from flask and pack in the bottle of sealing standby.
The parts by weight proportioning of the raw material that the DeR of described step 2 used in the stage is: 16 parts of alcoholysis agent, 48 parts of spandex waste silks and 0.16 part of DeR catalyzer.
The parts by weight proportioning of the raw material that in described step 3, the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives uses is: 20 parts of spandex waste silk part degraded product dibasic alcohol, 25 parts of polyester polyol CMA-44,8 parts of poly-hexanodioic acid 1.4-butanediol ester glycol, 39 parts of diphenylmethane isocyanate, 0.14 part of moisture curing catalytic reaction, 0.14 portion of viscosity stabilizer and 0.1 part of oxidation inhibitor.
Embodiment 2
Utilize spandex waste silk to prepare the method for the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, step is as follows:
Step 1: pretreatment stage, be about to spandex waste silk and through fiber pulverizer, be ground into the spandex waste silk of desired length, the spandex waste silk of desired length is just spandex waste silk to be added like this;
Step 2: DeR stage, the raw material using in stage in this DeR is alcoholysis agent, catalyzer and the spandex waste silk to be added that obtains in step 1 for DeR, first in the three-necked bottle of agitator and prolong is housed, first according to default alcoholysis agent, in the parts by weight ratio range dealing three-necked bottle with spandex waste silk to be added, add alcoholysis agent, this alcoholysis agent is ethylene glycol, subsequently the alcoholysis agent in three-necked bottle is carried out to heat temperature raising, heat temperature raising is until temperature is 180 ℃, again in spandex waste silk to be added, 1/10 the spandex waste silk that part by weight is accounted for to spandex waste silk to be added adds in three-necked bottle, follow according to default DeR the parts by weight ratio range with the raw material using in the shared DeR of the catalyzer stage, in three-necked bottle, add DeR catalyzer, described DeR catalyzer is zinc acetate, then with agitator, the raw material adding in three-necked bottle is carried out to the DeR under constant temperature stirring, in DeR process, in three-necked bottle, add remaining spandex waste silk to be added in batches, the reaction solution viscosity that is accompanied by the dissolving of spandex waste silk like this when DeR and carries out DeR in three-necked bottle also increases, according to the increase of reaction solution viscosity, by default speed, accelerate stirring reaction, when the reaction solution hydroxyl value that stirring reaction forms through DeR after four hours and in three-necked bottle is stabilized in default scope, stop stirring reaction, after the reaction solution in three-necked bottle is cooled to temperature to be 100 ℃, with 100 object filtering nets, the reaction solution in three-necked bottle is carried out to filtered while hot, reaction solution after filtered while hot is cooled to the yellow thick liquid obtaining after normal temperature, be spandex waste silk degraded product dibasic alcohol, this DeR product is sealed and saved backup,
Step 3: the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, the raw material using at the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is vulcabond, moisture curing catalysts, oxidation inhibitor, viscosity stabilizer, the spandex waste silk degraded product dibasic alcohol and the polyester polyol that in step 2, obtain, polyether glycol, be about to polyester polyol, polyether glycol joins and in flask, forms mixture by the parts by weight ratio range of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives with the spandex waste silk degraded product dibasic alcohol obtaining in step 2, polyester polyol is that polyester polyol CMA-44 and poly-hexanodioic acid 1.4-butanediol ester glycol are mixed to form, after this mixture is stirred with agitator, after mixture in this flask is warming up to temperature and is 130 ℃, then this mixture is carried out to vacuum hydro-extraction 3 hours, then the mixture after vacuum hydro-extraction being cooled to temperature is 80 ℃, in flask, pass into nitrogen protection, by the parts by weight scope of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, in the mixture after vacuum hydro-extraction, add vulcabond simultaneously, this vulcabond is terephthalylidene vulcabond, and to having added the mixture of vulcabond to stir according to default speed with agitator, in whipping process, carry out the building-up reactions of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, after the lasting 2h of stirring, obtain the Primary product of building-up reactions, parts by weight ratio range by the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives adds moisture curing catalysts, oxidation inhibitor involutoryly becomes the Primary product of reaction to carry out obtaining the glutinous agent of synthetic One-Component Moisture-Curable Polyurethane Hot Melt Adhesives after building-up reactions 20min with continuing after viscosity stabilizer, this moisture curing catalysts is dibutyl tin laurate, the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is poured out from flask and pack in the bottle of sealing standby.
The parts by weight proportioning of the raw material that the DeR of described step 2 used in the stage is: 16 parts of alcoholysis agent, 32 parts of spandex waste silks and 0.1 part of DeR catalyzer.
The parts by weight proportioning of the raw material that in described step 3, the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives uses is: 20 parts of spandex waste silk part degraded product dibasic alcohol, 30 parts of polyester polyol CMA-44,10 parts of poly-hexanodioic acid 1.4-butanediol ester glycol, 30 parts of terephthalylidene vulcabond, 0.13 part of moisture curing catalysts, 0.1 portion of viscosity stabilizer and 0.1 part of oxidation inhibitor.
Embodiment 3
Utilize spandex waste silk to prepare the method for the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, step is as follows:
Step 1: pretreatment stage, be about to spandex waste silk and through fiber pulverizer, be ground into the spandex waste silk of desired length, the spandex waste silk of desired length is just spandex waste silk to be added like this;
Step 2: DeR stage, the raw material using in stage in this DeR is alcoholysis agent, catalyzer and the spandex waste silk to be added that obtains in step 1 for DeR, first in the three-necked bottle of agitator and prolong is housed, first according to default alcoholysis agent, in the parts by weight ratio range dealing three-necked bottle with spandex waste silk to be added, add alcoholysis agent, this alcoholysis agent is 1, 4-butyleneglycol, subsequently the alcoholysis agent in three-necked bottle is carried out to heat temperature raising, heat temperature raising is until temperature is 180 ℃, again in spandex waste silk to be added, 1/10 the spandex waste silk that part by weight is accounted for to spandex waste silk to be added adds in three-necked bottle, follow according to default DeR the parts by weight ratio range with the raw material using in the shared DeR of the catalyzer stage, in three-necked bottle, add DeR catalyzer, described DeR catalyzer is potassium acetate, then with agitator, the raw material adding in three-necked bottle is carried out to the DeR under constant temperature stirring, in DeR process, in three-necked bottle, add remaining spandex waste silk to be added in batches, the reaction solution viscosity that is accompanied by the dissolving of spandex waste silk like this when DeR and carries out DeR in three-necked bottle also increases, according to the increase of reaction solution viscosity, by default speed, accelerate stirring reaction, when the reaction solution hydroxyl value that stirring reaction forms through DeR after four hours and in three-necked bottle is stabilized in default scope, stop stirring reaction, after the reaction solution in three-necked bottle is cooled to temperature to be 100 ℃, with 100 object filtering nets, the reaction solution in three-necked bottle is carried out to filtered while hot, reaction solution after filtered while hot is cooled to the yellow thick liquid obtaining after normal temperature, be spandex waste silk degraded product dibasic alcohol, this DeR product is sealed and saved backup,
Step 3: the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, the raw material using at the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is vulcabond, moisture curing catalysts, oxidation inhibitor, viscosity stabilizer, the spandex waste silk degraded product dibasic alcohol and the polyester polyol that in step 2, obtain, polyether glycol, be about to polyester polyol, polyether glycol joins and in flask, forms mixture by the parts by weight ratio range of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives with the spandex waste silk degraded product dibasic alcohol obtaining in step 2, polyester polyol is that the poly-hexanodioic acid 1.4-butanediol ester glycol of polyester polyol CMA-44 and 8g is mixed to form, after this mixture is stirred with agitator, after mixture in this flask is warming up to temperature and is 130 ℃, then this mixture is carried out to vacuum hydro-extraction 3 hours, then the mixture after vacuum hydro-extraction being cooled to temperature is 80 ℃, in flask, pass into nitrogen protection, by the parts by weight scope of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, in the mixture after vacuum hydro-extraction, add vulcabond simultaneously, this vulcabond is diphenylmethanediisocyanate, and to having added the mixture of vulcabond to stir according to default speed with agitator, in whipping process, carry out the building-up reactions of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, after the lasting 2h of stirring, obtain the Primary product of building-up reactions, parts by weight ratio range by the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives adds moisture curing catalysts, oxidation inhibitor involutoryly becomes the Primary product of reaction to carry out obtaining the glutinous agent of synthetic One-Component Moisture-Curable Polyurethane Hot Melt Adhesives after building-up reactions 20min with continuing after viscosity stabilizer, this moisture curing catalysts is dibutyl tin laurate, the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is poured out from flask and pack in the bottle of sealing standby.
The parts by weight proportioning of the raw material that the DeR of described step 2 used in the stage is: 16 parts of alcoholysis agent, 48 parts of spandex waste silks and 0.3 part of DeR catalyzer.
The parts by weight proportioning of the raw material that in described step 3, the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives uses is: 20 parts of spandex waste silk part degraded product dibasic alcohol, 30 parts of CMA-44 and 10 parts of poly-hexanodioic acid 1.4-butanediol ester glycol, 33 parts of diphenylmethanediisocyanates, 0.14 part of moisture curing catalysts, 0.14 portion of viscosity stabilizer and 0.1 part of oxidation inhibitor.
Embodiment 4
Utilize spandex waste silk to prepare the method for the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, step is as follows:
Step 1: pretreatment stage, be about to spandex waste silk and through fiber pulverizer, be ground into the spandex waste silk of desired length, the spandex waste silk of desired length is just spandex waste silk to be added like this;
Step 2: DeR stage, the raw material using in stage in this DeR is alcoholysis agent, catalyzer and the spandex waste silk to be added that obtains in step 1 for DeR, first in the three-necked bottle of agitator and prolong is housed, first according to default alcoholysis agent, in the parts by weight ratio range dealing three-necked bottle with spandex waste silk to be added, add alcoholysis agent, this alcoholysis agent is 1.3-propylene glycol, subsequently the alcoholysis agent in three-necked bottle is carried out to heat temperature raising, heat temperature raising is until temperature is 180 ℃, again in spandex waste silk to be added, 1/10 the spandex waste silk that part by weight is accounted for to spandex waste silk to be added adds in three-necked bottle, follow according to default DeR the parts by weight ratio range with the raw material using in the shared DeR of the catalyzer stage, in three-necked bottle, add DeR catalyzer, described DeR catalyzer is potassium acetate, then with agitator, the raw material adding in three-necked bottle is carried out to the DeR under constant temperature stirring, in DeR process, in three-necked bottle, add remaining spandex waste silk to be added in batches, the reaction solution viscosity that is accompanied by the dissolving of spandex waste silk like this when DeR and carries out DeR in three-necked bottle also increases, according to the increase of reaction solution viscosity, by default speed, accelerate stirring reaction, when the reaction solution hydroxyl value that stirring reaction forms through DeR after four hours and in three-necked bottle is stabilized in default scope, stop stirring reaction, after the reaction solution in three-necked bottle is cooled to temperature to be 100 ℃, with 100 object filtering nets, the reaction solution in three-necked bottle is carried out to filtered while hot, reaction solution after filtered while hot is cooled to the yellow thick liquid obtaining after normal temperature, be spandex waste silk degraded product dibasic alcohol, this DeR product is sealed and saved backup,
Step 3: the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, the raw material using at the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is vulcabond, moisture curing catalysts, oxidation inhibitor, viscosity stabilizer, the spandex waste silk degraded product dibasic alcohol and the polyester polyol that in step 2, obtain, polyether glycol, be about to polyester polyol, polyether glycol joins and in flask, forms mixture by the parts by weight ratio range of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives with the spandex waste silk degraded product dibasic alcohol obtaining in step 2, polyester polyol is that polyester polyol CMA-44 and poly-hexanodioic acid 1.4-butanediol ester glycol are mixed to form, after this mixture is stirred with agitator, after mixture in this flask is warming up to temperature and is 130 ℃, then this mixture is carried out to vacuum hydro-extraction 3 hours, then the mixture after vacuum hydro-extraction being cooled to temperature is 80 ℃, in flask, pass into nitrogen protection, by the parts by weight scope of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, in the mixture after vacuum hydro-extraction, add vulcabond simultaneously, this vulcabond is diphenylmethanediisocyanate, and to having added the mixture of vulcabond to stir according to default speed with agitator, in whipping process, carry out the building-up reactions of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, after the lasting 2h of stirring, obtain the Primary product of building-up reactions, parts by weight ratio range by the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives adds moisture curing catalysts, oxidation inhibitor involutoryly becomes the Primary product of reaction to carry out obtaining the glutinous agent of synthetic One-Component Moisture-Curable Polyurethane Hot Melt Adhesives after building-up reactions 20min with continuing after viscosity stabilizer, this moisture curing catalysts is dibutyl tin laurate, the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is poured out from flask and pack in the bottle of sealing standby.
The parts by weight proportioning of the raw material that the DeR of described step 2 used in the stage is: 16 parts of alcoholysis agent, 64 parts of spandex waste silks and 0.48 part of DeR catalyzer.
The parts by weight proportioning of the raw material that in described step 3, the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives uses is: 25 parts of spandex waste silk part degraded product dibasic alcohol, 30 parts of polyester polyol CMA-44,8 parts of poly-hexanodioic acid 1.4-butanediol ester glycol, 45 parts of diphenylmethanediisocyanates, 0.13 part of moisture curing catalysts, 0.13 portion of viscosity stabilizer and 0.1 part of oxidation inhibitor.
Claims (8)
1. utilize spandex waste silk to prepare a method for the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, it is characterized in that, step is as follows:
Step 1: pretreatment stage, be about to spandex waste silk and through fiber pulverizer, be ground into the spandex waste silk of desired length, the spandex waste silk of desired length is just spandex waste silk to be added like this;
Step 2: DeR stage, the raw material using in stage in this DeR is alcoholysis agent, catalyzer and the spandex waste silk that obtains in step 1 for DeR, first in the three-necked bottle of agitator and prolong is housed, elder generation is the parts by weight proportioning with spandex waste silk to be added according to default alcoholysis agent, in three-necked bottle, add alcoholysis agent, subsequently the alcoholysis agent in three-necked bottle is carried out to heat temperature raising, heat temperature raising is until temperature is 180-200 ℃, 1/10 the spandex waste silk that part by weight is accounted for to spandex waste silk to be added adds in three-necked bottle, follow according to default DeR the parts by weight ratio range with the raw material using in the shared DeR of the catalyzer stage, in three-necked bottle, add DeR catalyzer, then with agitator, the raw material adding in three-necked bottle is carried out to the DeR under constant temperature stirring, in DeR process, in three-necked bottle, add remaining spandex waste silk to be added in batches, the reaction solution viscosity that is accompanied by the dissolving of spandex waste silk like this when DeR and carries out DeR in three-necked bottle also increases, according to the increase of reaction solution viscosity, by default speed, accelerate stirring reaction, when the reaction solution hydroxyl value that stirring reaction forms through DeR after four hours and in three-necked bottle is stabilized in default scope, stop stirring reaction, after the reaction solution in three-necked bottle is cooled to temperature range to be 95 ℃-105 ℃, with 100 ~ 120 object filtering nets, the reaction solution in three-necked bottle is carried out to filtered while hot, reaction solution after filtered while hot is cooled to the yellow thick liquid obtaining after normal temperature, be spandex waste silk degraded product dibasic alcohol, this DeR product is sealed and saved backup,
Step 3: the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, the raw material using at the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is vulcabond, moisture curing catalysts, oxidation inhibitor, viscosity stabilizer, the spandex waste silk degraded product dibasic alcohol and the polyester polyol that in step 2, obtain, polyether glycol, be about to polyester polyol, polyether glycol joins and in flask, forms mixture by the parts by weight proportioning of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives with the spandex waste silk degraded product dibasic alcohol obtaining in step 2, after this mixture is stirred with agitator, after mixture in this flask is warming up to temperature range and is 120 ~ 130 ℃, then this mixture is carried out to vacuum hydro-extraction 2-3 hour, then the mixture after vacuum hydro-extraction being cooled to temperature range is 70-80 ℃, in flask, pass into nitrogen protection, by the parts by weight scope of the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, in the mixture after vacuum hydro-extraction, add vulcabond simultaneously, and to having added the mixture of vulcabond to stir according to default speed with agitator, in whipping process, carry out the building-up reactions of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives, after the lasting 2h of stirring, obtain the Primary product of building-up reactions, parts by weight ratio range by the raw material using in the synthesis phase of the glutinous agent of default shared One-Component Moisture-Curable Polyurethane Hot Melt Adhesives adds moisture curing catalysts, oxidation inhibitor involutoryly becomes the Primary product of reaction to carry out obtaining the glutinous agent of synthetic One-Component Moisture-Curable Polyurethane Hot Melt Adhesives after building-up reactions 20min with continuing after viscosity stabilizer, the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives is poured out from flask and pack in the bottle of sealing standby,
The parts by weight proportioning of the raw material that the DeR of described step 2 used in the stage is: 16-33 part alcoholysis agent, 33-80 part spandex waste silk and 0.2-0.5 part DeR catalyzer;
The parts by weight proportioning of the raw material that in described step 3, the synthesis phase of the glutinous agent of this One-Component Moisture-Curable Polyurethane Hot Melt Adhesives uses is: 20-28 part spandex waste silk part degraded product dibasic alcohol, 18-34 part polyester polyol, 5-12 part polyether glycol, 30 ~ 45 parts of vulcabond, 0.1 ~ 0.15 part of moisture curing catalysts, 0.1 ~ 0.15 portion of viscosity stabilizer and 0.1 ~ 0.5 part of oxidation inhibitor.
2. the method for utilizing spandex waste silk to prepare the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives according to claim 1, is characterized in that, the alcoholysis agent in described step 2 is the polyvalent alcohol of 2-10 carbon atom.
3. the spandex waste silk that utilizes according to claim 2 is prepared the method that One-Component Moisture-Curable Polyurethane Hot Melt Adhesives sticks agent, it is characterized in that, the polyvalent alcohol of a described 2-10 carbon atom comprises ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, glycol ether, Triethylene glycol, tetraethylene-glycol, glycerol, low-molecular-weight polyethers or polyester polyol.
4. according to claim 1 or the method for utilizing spandex waste silk to prepare the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives claimed in claim 2, it is characterized in that, described DeR used catalyst is zinc acetate, tin tetrachloride, stannous octoate, triethylamine or dibutyl tin laurate, also can adopt tin tetrachloride, stannous octoate, triethylamine, dibutyl tin laurate to be combined with each other and to form DeR used catalyst according to default ratio.
5. according to claim 1 or the method for utilizing spandex waste silk to prepare the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives claimed in claim 2, the polyester polyol in the step 3 described in it is characterized in that in the synthesis phase of the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives and the molecular weight of polyether glycol are in 1000～5000 scopes.
6. according to claim 1 or the method for utilizing spandex waste silk to prepare the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives claimed in claim 2, it is characterized in that described vulcabond comprises aromatic series, aliphatics and alicyclic diisocyanate.
7. the spandex waste silk that utilizes according to claim 6 is prepared the method that One-Component Moisture-Curable Polyurethane Hot Melt Adhesives sticks agent, it is characterized in that, described vulcabond comprises tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), the mixture of one or more in isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI).
8. according to claim 1 or the method for utilizing spandex waste silk to prepare the glutinous agent of One-Component Moisture-Curable Polyurethane Hot Melt Adhesives claimed in claim 2, it is characterized in that described moisture curing catalysts is one or more the composite uses in organic tin, organo-bismuth class or amine.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368079A (en) * | 2008-09-25 | 2009-02-18 | 广州市鹿山化工材料有限公司 | Polyurethane hot melt adhesive with fast crystallization and preparation method thereof |
| CN102219888A (en) * | 2011-05-30 | 2011-10-19 | 上海联景高分子材料有限公司 | Process for manufacturing thermoplastic urethane (TPU) by utilizing waste spandex fiber |
| CN102796279A (en) * | 2012-08-16 | 2012-11-28 | 上海翌能化工科技有限公司 | Method for recovery of polyurethane through alcoholysis |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368079A (en) * | 2008-09-25 | 2009-02-18 | 广州市鹿山化工材料有限公司 | Polyurethane hot melt adhesive with fast crystallization and preparation method thereof |
| CN102219888A (en) * | 2011-05-30 | 2011-10-19 | 上海联景高分子材料有限公司 | Process for manufacturing thermoplastic urethane (TPU) by utilizing waste spandex fiber |
| CN102796279A (en) * | 2012-08-16 | 2012-11-28 | 上海翌能化工科技有限公司 | Method for recovery of polyurethane through alcoholysis |
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