CN100494301C - Nano polyurethane adhesive and its preparation process - Google Patents
Nano polyurethane adhesive and its preparation process Download PDFInfo
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- CN100494301C CN100494301C CNB2005100474511A CN200510047451A CN100494301C CN 100494301 C CN100494301 C CN 100494301C CN B2005100474511 A CNB2005100474511 A CN B2005100474511A CN 200510047451 A CN200510047451 A CN 200510047451A CN 100494301 C CN100494301 C CN 100494301C
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Abstract
This invention involves a nano-modified polyurethane adhesive materials and fabrication methods, which include the following components (weight ratio) : hydroxy-terminated polyester 60~80; isocyanate 3~10; chain extender 1~3; mixed solvent 200~400; Nanomaterials 1~3; catalyst 0.02~0.4; inhibitor 0.01. Preparation method: (1)add adipic acid, 1,4-butanediol into reactor, the temperature to 140 deg.C, add catalyst, control tower fractionation temperature 100~102 deg.C; (2) When the fractionation tower temperature less than 80 deg.C, gradually warming up to 210 deg.C, keep temperature under the protection of nitrogen; (3) evacuation under the reaction temperature of 210 deg. C; (4) add polyester into mixing reactor; (5) add isocyanates; (6) add catalyst for the shares, stir; (7) add nano-materials, stirring.
Description
Technical field
The present invention relates to a kind of nano material modified polyurethane tackiness agent and preparation method thereof.
Background technology
Urethane is that a class is soft section with oligomeric polyols, isocyanic ester and chainextender are the block compound of hard section, contain various polarity keys such as amino-formate bond, ester bond, urea key and allophanic acid ester bond in its chemical structure, given its superior adhesiveproperties and film forming properties.Being specially adapted to the other types tackiness agent can not bonding or bonding inconvenient place.It with contain the material of reactive hydrogen, as the material of any surface finish such as porous material such as porous plastics, timber, leather, fabric, paper, pottery and metal, glass, rubber, plastics the excellent in chemical bounding force is arranged all.Just because of this good adhesiveproperties of polyurethane adhesive with to the bonding adaptability of multiple base material, its Application Areas is constantly enlarged, at home and abroad development in recent years is very fast, becomes one of important kind in the eight big synthetic adhesives.
Calendar year 2001, polyurethane adhesive demand in West Europe was 12.3 ten thousand tons, expected tackiness agent output in 2006 and will reach 16.67 ten thousand tons, and average annual the growth is 1.9%.China's polyurethane adhesive industry and scale grew a lot in recent years, and state of the art also improves constantly, but with to compare gap abroad still bigger, the shoes-used glue of application quantity maximum needs import more than 95%.And China polyurethane adhesive manufacturer scale is less, and kind is single, products production batch poor stability, and the state of the art of product and use properties are badly in need of further improving.Simultaneously, the most of neoprene latex that uses of China's shoe industry, its not plasticizer-resistant infiltration, poor to novel footwear such as soft pvc, thermoplastic elastomer, PU leather with material adhesive, must use benzene class noxious solvent, incompatibility shoemaking industry demand for development.Along with perfecting day by day of Environmental Protection in China rules, and the raising of people self health perception, good, the free of contamination environmental-protection type adhesive of quality is becoming the main product of synthetic adhesive, and development prospect is wide.
Simultaneously, nano material and nano composite material are a kind of novel high-performance materials that develops rapidly over nearly 20 years.Because its tempting feature at aspects such as structure, photoelectricity and chemical property has caused material supply section scholar's great interest.Along with the continuous development and the maturation of nano material preparation technology, people can prepare various types of nano materials of different-grain diameter, different components, different structure easily, for solid basis has been established in the development and application of nano material.
Summary of the invention
Technical solution of the present invention can realize according to following mode:
Nano polyurethane adhesive, it comprises following component (mass ratio):
Hydroxyl telechelic polyester 60～80
Isocyanic ester 3～10
Chainextender 1～3
Mixed solvent 200～400
Nano material (mineral filler) 1～3
Catalyzer 0.02～0.4
Stopper 0.01.
Hydroxyl telechelic polyester of the present invention is that molecular-weight average is 2000～3000 the poly-hexanodioic acid-1 of terminal hydroxy group, 4-butanediol ester glycol, molecular-weight average is 3000～5000 poly-hexanodioic acid-1,6-hexylene glycol esterdiol, molecular-weight average is 2500～4000 poly-hexanodioic acid-1,4-butyleneglycol/1,6 hexylene glycol esterdiol; Described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, 1,6-hexamethylene diisocyanate; Described chainextender is 1,4-butyleneglycol or 1,6-hexylene glycol; Described nano material is through chemical modification or without the nano level CaSO4 whisker or the nano level CaCO3 particle of chemical modification; Described catalyzer is tin class catalyzer or amines catalyst; Described stopper is a Benzoyl chloride; Described mixed solvent is that butanone, acetone, ethyl acetate mix by mass fraction 25:30:30.
The preparation technology of one-part solvent type nano polyurethane adhesive of the present invention is followed successively by:
(1) take by weighing hexanodioic acid by acid alcohol mol ratio 1:1.0～1.2,1, the 4-butyleneglycol joins in the reactor, in 60 minutes, be warming up to 140 ℃, add the catalyzer that accounts for reaction system total mass 1 ‰, under the nitrogen protection condition, stir, divide water, and between 100～102 ℃ of the control cat head cut points;
(2) when cat head cut point during less than 80 ℃, beginning heats up gradually, and the control reaction divides water, during to 210 ℃ of temperature of reaction, is incubated 2～3 hours under the nitrogen protection condition;
(3) under 210 ℃ of temperature of reaction, vacuumize gradually from low to high, to the product acid number less than 1mgKOH/g, hydroxyl value 30～120mgKOH/g is qualified polyester;
(4) take by weighing the prescription required umber the polyester after vacuum hydro-extraction join in the stirred reactor, be warming up to 80 ℃;
(5) isocyanic ester of the required umber of adding stirs rapidly, to stirring at need, adds mixed solvent gradually;
(6) add required umber catalyzer, under 60～80 ℃ of temperature condition, stirred 1 hour;
(7) nano material of the drying processing of the required umber of adding stirred 1 hour under 60～80 ℃ of conditions;
(8) stopper of the required umber of adding stirred 10 minutes;
(9) through check, pack sebific duct into and make finished product.
When above-mentioned isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water, to add again after the fusing.
The present invention also provides the another kind of preparation method of one-part solvent type footwear with nano polyurethane adhesive, and its preparation technology is followed successively by:
(1) takes by weighing diprotic acid by acid alcohol mol ratio 1:1.0～1.2 and dibasic alcohol joins in the reactor, in 60min, be warming up to 140 ℃, add the catalyzer that accounts for reaction system total mass 1 ‰, under the nitrogen protection condition, stir, divide water, and control cat head cut point is between 100～102 ℃;
(2) when cat head cut point during less than 80 ℃, beginning heats up gradually, and the control reaction divides water, during to 210 ℃ of temperature of reaction, is incubated 2～3h under the nitrogen protection condition;
(3) under 210 ℃ of temperature of reaction, vacuumize gradually from low to high, to the product acid number less than 1mgKOH/g, during hydroxyl value 30～120mgKOH/g, be qualified polyester;
(4) take by weighing the prescription required umber the polyester after vacuum hydro-extraction join in the reactor, be warming up to 80 ℃;
(5) chainextender through distillation dehydration of the required umber of adding mixes;
(6) isocyanic ester of the required umber of adding stirs rapidly, to stirring at need, adds mixed solvent gradually;
(7) add required umber catalyzer, under 60～80 ℃ of conditions, stirred 1 hour;
(8) nano material of the drying processing of the required umber of adding stirred 1 hour under 60～80 ℃ of conditions;
(9) stopper of the required umber of adding stirred 10 minutes;
(10) through check, pack sebific duct into and make finished product.
When above-mentioned isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water, to add again after the fusing.
Compared with prior art, advantage of the present invention is:
1) solvent in the component prescription is low toxicity or innoxious solvent, and environment and production, user's health is not had harm.
2) nano material is joined the density that has increased cross-linking set in the glue, make microphase-separated complete, thereby toughness, tack and the stripping strength of polyurethane adhesive are all increased.
3) adopt solution method to join glue, operating procedure is simple, and constant product quality can realize suitability for industrialized production.
Embodiment
Processing step of the present invention is described by the following examples, but not limited by embodiment.
Embodiment 1
Press following prescription and prepared one-part solvent type footwear nano polyurethane adhesive:
Prescription:
Hydroxyl telechelic polyester is that molecular-weight average is 2500 the poly-hexanodioic acid-1 of terminal hydroxy group, 4-butanediol ester glycol;
Isocyanic ester is a tolylene diisocyanate;
Solvent is mixed solvent (butanone, acetone, ethyl acetate are pressed mass fraction 25:30:30 and mixed);
Nano filling is 200 nano level CaSO4 whiskers without chemical modification;
Catalyzer is a dibutyl tin laurate;
Stopper is a Benzoyl chloride;
Preparation technology:
(1) take by weighing hexanodioic acid 400g and corresponding 1 by acid alcohol mol ratio 1:1.0～1.2, the 4-butyleneglycol joins in the reactor, is warming up to 140 ℃ in 60 minutes; add catalyzer 0.6g; under the nitrogen protection condition, stir, divide water, and control cat head cut point is between 100～102 ℃.
(2) when cat head cut point during less than 80 ℃, beginning heats up gradually, and the control reaction divides water, during to 210 ℃ of temperature of reaction, is incubated 2～3 hours under the nitrogen protection condition.
(3) under 210 ℃ of temperature of reaction, vacuumize gradually from low to high, to the product acid number less than 1mgKOH/g, during hydroxyl value 30～120mgKOH/g, be qualified polyester.
(4) take by weighing the polyester of 100g after vacuum hydro-extraction and join in the reactor, be warming up to 80 ℃.
(5) isocyanic ester of adding 9.80g (R=0.98) stirs rapidly, to stirring at need, adds mixed solvent gradually.
(6) catalyzer of adding 0.1g stirred 1 hour under 60～80 ℃ of conditions.
(7) add 2g at 200 ℃ of drying treatment 2h, through the 200 nano level CaSO4 whiskers of ultrasonic dispersing 20min, under 60～80 ℃ of conditions, stirred 1 hour without chemical modification.
(8) stopper of adding 0.01g stirred 10 minutes.
(9) through check, pack sebific duct into and make finished product.
By the one-part solvent type polyurethane in use for shoes tackiness agent that above-mentioned prescription and technology make, its performance physical and chemical index and as shown in the table with the index value contrast of domestic like product:
(PVC leather-PVC leather):
Embodiment 2
By following prescription and prepared one-part solvent type footwear nano polyurethane adhesive
Prescription:
Hydroxyl telechelic polyester is that molecular-weight average is 3000 the poly-hexanodioic acid-1 of terminal hydroxy group, 4-butyleneglycol/1,6-hexylene glycol esterdiol;
Isocyanic ester is a diphenylmethanediisocyanate;
Chainextender is 1, the 4-butyleneglycol;
Solvent is mixed solvent (butanone, acetone, ethyl acetate are pressed mass fraction 25:30:30 and mixed);
Nano filling is 200 nano level CaSO4 whiskers of chemical modification;
Catalyzer is a dibutyl tin laurate;
Stopper is a Benzoyl chloride;
Preparation technology:
(1) takes by weighing hexanodioic acid 400g and corresponding 1 by acid alcohol mol ratio 1:1.0～1.2,4-butyleneglycol and 1,6-hexylene glycol (mol ratio is 1:3) joins in the reactor, in 60min, be warming up to 140 ℃, add catalyzer 0.6g, under the nitrogen protection condition, stir, divide water, and control cat head cut point is between 100～102 ℃;
(2) when cat head cut point during less than 80 ℃, beginning heats up gradually, and the control reaction divides water, during to 210 ℃ of temperature of reaction, is incubated 2～3 hours under the nitrogen protection condition;
(3) under 210 ℃ of temperature of reaction, vacuumize gradually from low to high, to the product acid number less than 1mgKOH/g, during hydroxyl value 30～120mgKOH/g, be qualified polyester;
(4) take by weighing the polyester of 100g after vacuum hydro-extraction and join in the reactor, be warming up to 80 ℃;
(5) add the chainextender of 1.20g, mix through distillation dehydration;
(6) isocyanic ester of adding 9.31g stirs rapidly, to stirring at need, adds mixed solvent gradually;
(7) catalyzer of adding 0.1g stirred 1 hour under 60～80 ℃ of conditions;
(8) add 2g 120 ℃ of drying treatment 2 hours, through 200 nano level CaSO4 whiskers of 20 minutes chemical modification of ultrasonic dispersing, under 60～80 ℃ of conditions, stirred 1 hour;
(9) stopper of adding 0.01g stirred 10 minutes;
(10) through check, pack sebific duct into and make finished product.
By the one-part solvent type polyurethane in use for shoes tackiness agent that above-mentioned prescription and technology make, its performance physical and chemical index and as shown in the table with the index value contrast of domestic like product:
(PVC leather-PVC leather):
Embodiment 3
By following prescription and prepared one-part solvent type footwear nano polyurethane adhesive
Prescription:
Hydroxyl telechelic polyester is that molecular-weight average is 2500 the poly-hexanodioic acid-1 of terminal hydroxy group, 6-hexylene glycol esterdiol
Isocyanic ester is 1,6-hexamethylene diisocyanate;
Chainextender is 1, the 4-butyleneglycol;
Solvent is mixed solvent (butanone, acetone, ethyl acetate are pressed mass fraction 25:30:30 and mixed);
Nano filling is without chemically treated nano level (＜100nm=CaCO3 particle;
Catalyzer is a diethanolamine;
Stopper is a Benzoyl chloride;
Preparation technology:
(1) take by weighing hexanodioic acid 400g and corresponding 1 by acid alcohol mol ratio 1:1.0～1.2, the 6-hexylene glycol joins in the reactor, is warming up to 140 ℃ in 60 minutes, add catalyzer 0.6g, under the nitrogen protection condition, stir, divide water, and control cat head cut point is between 100～102 ℃;
(2) when cat head cut point during less than 80 ℃, beginning heats up gradually, and the control reaction divides water, during to 210 ℃ of temperature of reaction, is incubated 2～3 hours under the nitrogen protection condition;
(3) under 210 ℃ of temperature of reaction, vacuumize gradually from low to high, to the product acid number less than 1mgKOH/g, during hydroxyl value 30～120mgKOH/g, be qualified polyester;
(4) take by weighing the polyester of 100g after vacuum hydro-extraction and join in the reactor, be warming up to 80 ℃;
(5) add the chainextender of 1.22g, mix through distillation dehydration;
(6) isocyanic ester of adding 3.35g (R=0.995) stirs rapidly, to stirring at need, adds mixed solvent gradually;
(7) catalyzer of adding 0.1g stirred 1 hour under 60～80 ℃ of conditions;
(8) add 2g at 200 ℃ of drying treatment 2h, through ultrasonic dispersing 20 minutes without chemically treated nano level (＜100nm=CaCO3 particle), under 60～80 ℃ of conditions, stirred 1 hour;
(9) stopper of adding 0.01g stirred 10 minutes;
(10) through check, pack sebific duct into and make finished product.
By the one-part solvent type polyurethane in use for shoes tackiness agent that above-mentioned prescription and technology make, its performance physical and chemical index and as shown in the table with the index value contrast of domestic like product:
(PVC leather-PVC leather):
Claims (3)
1, nano polyurethane adhesive is characterized in that, comprises following component by quality ratio:
Hydroxyl telechelic polyester 60～80
Isocyanic ester 3～10
Chainextender 1～3
Mixed solvent 200～400
Nano material 1～3
Catalyzer 0.02～0.4
Stopper 0.01;
Described hydroxyl telechelic polyester is that molecular-weight average is 2000～3000 the poly-hexanodioic acid-1 of terminal hydroxy group, 4-butanediol ester glycol, molecular-weight average is 3000～5000 poly-hexanodioic acid-1,6-hexylene glycol esterdiol, molecular-weight average is 2500～4000 poly-hexanodioic acid-1,4-butyleneglycol/1,6 hexylene glycol esterdiol; Described isocyanic ester is tolylene diisocyanate, diphenylmethanediisocyanate, isoflurane chalcone diisocyanate, 1,6-hexamethylene diisocyanate; Described chainextender is 1,4-butyleneglycol or 1,6-hexylene glycol; Described nano material is through chemical modification or without the nano level CaSO4 whisker or the nano level CaCO3 particle of chemical modification; Described catalyzer is tin class catalyzer or amines catalyst; Described stopper is a Benzoyl chloride; Described mixed solvent is that butanone, acetone, ethyl acetate mix by mass fraction 25:30:30.
2, the preparation method of nano polyurethane adhesive according to claim 1 is characterized in that, implements as follows:
(1) take by weighing hexanodioic acid by acid alcohol mol ratio 1:1.0～1.2,1, the 4-butyleneglycol joins in the reactor, in 60 minutes, be warming up to 140 ℃, add the catalyzer that accounts for reaction system total mass 1 ‰, under the nitrogen protection condition, stir, divide water, and between 100～102 ℃ of the control cat head cut points;
(2) when cat head cut point during less than 80 ℃, beginning heats up gradually, and the control reaction divides water, during to 210 ℃ of temperature of reaction, is incubated 2～3 hours under the nitrogen protection condition;
(3) under 210 ℃ of temperature of reaction, vacuumize gradually from low to high, to the product acid number less than 1mgKOH/g, hydroxyl value 30～120mgKOH/g is qualified polyester;
(4) take by weighing the prescription required umber the polyester after vacuum hydro-extraction join in the stirred reactor, be warming up to 80 ℃;
(5) isocyanic ester of the required umber of adding stirs rapidly, to stirring at need, adds mixed solvent gradually;
(6) add required umber catalyzer, under 60～80 ℃ of temperature condition, stirred 1 hour;
(7) nano material of the drying processing of the required umber of adding stirred 1 hour under 60～80 ℃ of conditions;
(8) stopper of the required umber of adding stirred 10 minutes;
(9) through check, pack sebific duct into and make finished product;
When described isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water, to add again after the fusing.
3, the preparation method of nano polyurethane adhesive according to claim 1 is characterized in that, implements as follows:
(1) takes by weighing diprotic acid by acid alcohol mol ratio 1:1.0～1.2 and dibasic alcohol joins in the reactor, in 60 minutes, be warming up to 140 ℃, add the catalyzer that accounts for reaction system total mass 1 ‰, under the nitrogen protection condition, stir, divide water, and control cat head cut point is between 100～102 ℃;
(2) when cat head cut point during less than 80 ℃, beginning heats up gradually, and the control reaction divides water, during to 210 ℃ of temperature of reaction, is incubated 2～3 hours under the nitrogen protection condition;
(3) under 210 ℃ of temperature of reaction, vacuumize gradually from low to high, to the product acid number less than 1mgKOH/g, during hydroxyl value 30～120mgKOH/g, be qualified polyester;
(4) take by weighing the prescription required umber the polyester after vacuum hydro-extraction join in the reactor, be warming up to 80 ℃;
(5) chainextender through distillation dehydration of the required umber of adding mixes;
(6) isocyanic ester of the required umber of adding stirs rapidly, to stirring at need, adds mixed solvent gradually;
(7) add required umber catalyzer, under 60～80 ℃ of conditions, stirred 1 hour;
(8) nano material of the drying processing of the required umber of adding stirred 1 hour under 60～80 ℃ of conditions;
(9) stopper of the required umber of adding stirred 10 minutes;
(10) through check, pack sebific duct into and make finished product;
When described isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water, to add again after the fusing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100474511A CN100494301C (en) | 2005-10-19 | 2005-10-19 | Nano polyurethane adhesive and its preparation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100474511A CN100494301C (en) | 2005-10-19 | 2005-10-19 | Nano polyurethane adhesive and its preparation process |
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| Publication Number | Publication Date |
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| CN1955246A CN1955246A (en) | 2007-05-02 |
| CN100494301C true CN100494301C (en) | 2009-06-03 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002337B (en) * | 2010-10-21 | 2012-11-07 | 任廷茂 | High-strength aqueous polyurethane adhesive |
| CN102115657B (en) * | 2010-12-31 | 2013-05-15 | 广州鹿山新材料股份有限公司 | High-hardness quickly-setting polyurethane hot melt adhesive and preparation method thereof |
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