CN108300337A - No-solvent polyurethane adhesive used for textiles and preparation method thereof - Google Patents
No-solvent polyurethane adhesive used for textiles and preparation method thereof Download PDFInfo
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- CN108300337A CN108300337A CN201711304805.5A CN201711304805A CN108300337A CN 108300337 A CN108300337 A CN 108300337A CN 201711304805 A CN201711304805 A CN 201711304805A CN 108300337 A CN108300337 A CN 108300337A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
- C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of no-solvent polyurethane adhesives used for textiles and preparation method thereof, functional stuffing is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stirring adds foundational system in 35 minutes, 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.Obtained product can maintain peel strength in a long time, and be exposed to the variation for not causing aberration under ultraviolet light in a long time, have quite excellent anti-flammability.
Description
Technical field
The invention belongs to bonding agent fields, and in particular to a kind of no-solvent polyurethane adhesive used for textiles and its preparation side
Method.
Background technology
After the textile of burning and human contact, skin burn is gently then caused, heavy then threat to life, in textile combustion,
The health of a large amount of pernicious gases released also entail dangers to people, including such as carbon monoxide, hydrogen cyanide and aldehydes multiple gases are all
People can be caused to be choked to death to die.Adhesive for polyurethane the 1940s includes mainly polyisocyanic acid at first in German Industrial
Ester solvent glue, thermoplastic polyurethane solvent adhesive, the single, double component solvent glue of response type, no-solvent type, water-dispersion type, heat molten type are poly-
Urethane glue etc.；Its synthesis material and auxiliary agent type are various, can synthesize and make performance change range pole from MOLECULE DESIGN
Big serial adhesive can meet the requirement of different substrate materials bonding and use condition, and in the prior art, traditional fire retardant is mostly
Organophosphor or halogen containing flame-retardant, but the halogen content in the content of formaldehyde or fire retardant to dissociate in the textile after arranging
Height, do harm to huamn body, not environmentally, the processing discharge of pollutant are also relatively difficult.
Invention content
The object of the present invention is to provide a kind of preparation method of no-solvent polyurethane adhesive used for textiles, obtained product
It can be used in textile industry, have excellent peel strength, and be exposed under ultraviolet light do not cause aberration in a long time
Variation, especially have quite excellent flame retardant property and toughness.
To achieve the above object of the invention, the present invention adopts the following technical scheme that：
A kind of preparation method of no-solvent polyurethane adhesive used for textiles, includes the following steps：
(1) under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol and propionic acid are mixed；It is then refluxed for
Stirring 50 minutes, is then added ammonium hydroxide；Back flow reaction 40 minutes；Then it removes solvent and obtains solids；By solids in 500 DEG C
Then sintering 10 minutes calcines 15 minutes in 650 DEG C, grinds, washes, is dried to obtain functional stuffing；
(2) mix polyethylene alcohol solution, tetraphenylporphyrin iron, peroxidized t-butyl perbenzoate, 80 DEG C are stirred 3 hours,
Then water is removed, hexamethylene diisocyanate, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 is then added
Minute, glycerine is added, modified system is stirred to get；
(3) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, and 2- sulfydryls are then added
Pyridine, hexamethyl trien, 60 DEG C of stirrings add bisphenol A cyanate monomer for 1 hour and phthalic acid two contracts
Water glyceride, hexamethylene diisocyanate, 110 DEG C are stirred 15 minutes, and foundational system is obtained；
(4) functional stuffing is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stir 35 points
Clock adds foundational system, and 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
In the present invention, the ammoniacal liquor mass concentration is 20%.
In above-mentioned technical proposal, 2000 mesh sieve is crossed in step (1), after grinding, extracting screen underflow washing is dried to obtain function and fills out
Material；Solvent is removed using revolving method, is washed in the aqueous solution after washing not chloride ion-containing；Six ammonium chloroiridates, nitric hydrate nickel,
Cobalt nitrate, ethyl alcohol, propionic acid, ammonium hydroxide mass ratio be 35: 55: 10: 100: 30: 20.
In above-mentioned technical proposal, in step (2), the average molecular weight of polyvinyl alcohol is 4000~5000；Polyvinyl alcohol water
Solution, tetraphenylporphyrin iron, peroxidized t-butyl perbenzoate, hexamethylene diisocyanate, 1,3,5- three-glycidyls-S-
Triazinetrione, glycerine mass ratio be 100: 0.05: 2: 60: 30: 60.It is added while the present invention is by being added polyvinyl alcohol
Peroxidized t-butyl perbenzoate, tetraphenylporphyrin iron, realization reduce i.e. to polyvinyl alcohol the molecular weight of polyvinyl alcohol
Strand has certain degradation, after this is to follow-up several components mixing, improves the dispersion performance of polyvinyl alcohol and continuous
Performance has crucial help, especially avoids polyvinyl alcohol to the influence of overall performance, has given full play to polyvinyl alcohol and has improved function
Filler activity and increase compatibility, the effect of cementability.
In above-mentioned technical proposal, in step (3), diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 2- mercaptopyridines, six
Methyl trien, bisphenol A cyanate monomer, o-phthalic acid diglycidyl ester, hexamethylene diisocyanate
Mass ratio is 100: 25: 30: 8: 30: 20: 60: 60.
In above-mentioned technical proposal, in step (4), functional stuffing, modified system, ammonium thiocyanate, maleic anhydride, foundational system
Mass ratio be 5: 35: 3: 10: 100.
Adhesive for polyurethane has occurred thousands of kinds, and those skilled in the art know by using specific alcohol and spy
Fixed isocyanate compound can get the adhesive for polyurethane of different performance, methylene of the present invention as the raw material of polyurethane resin
Based structures are introduced into dispersions of polyurethanes molecule, can improve rate of drying, bonding force and the water resistance of adhesive for polyurethane,
Small molecule is suitably introduced into crosslinking to improve molecular weight, improves the long alkyl in the adhesive strength of adhesive, such as anacardol meta position
Chain has toughness, can effectively overcome brittleness with epoxy resin effect so that adhesive solidification temperature is low, solid with acid anhydrides mating reaction
Change soon, product cohesive force is strong.
The first public functional stuffing of the present invention is metal composite oxide, can be by promoting resin reaction to play increase
Resin bonding, water resistance effect, more important is the additions by functional stuffing to greatly improve resin system weatherability；
The defect that existing polyurethane resin belongs to " xanthochromia polyisocyanates " is efficiently solved, the heat-resisting temperature of adhesive can also be improved
Degree, and improve the mobility of adhesive；And the present invention is being added without phosphorus or halogen flame retardant by the addition of functional stuffing
In the case of, obtained adhesive flame retardant property is good, meets application requirement, and adhesive is also avoided by the cooperation of organic component
Glue surface will will present a large amount of graininess residual after coated, influence appearance yield, and to subsequently using causing unfavorable problem.
Prefabricated modified component is added in the present invention in base polyurethane material system, and obtained adhesive is in addition to polyurethane
Outside main body, also contain polyvinyl alcohol, while by the addition of small molecule polyvinyl alcohol not and be to separately exist in system, and
It is to be combined with polyurethane molecular chain, such as by the combination of isocyanates, to improve the stability of system；Pass through six
Methylene diisocyanate is reacted with several alcohol, and the polyurethane obtained first has excellent toughness, next solves existing
The hygroscopic problem of isocyanate group, and the presence of several alcohol improves the phase of polyvinyl alcohol, polyurethane and cyanate epoxy
Capacitive, especially under the limited promotion of metal oxide, obtained system reactivity is good, and (70 DEG C) heating of low temperature can be formed
Stable glue-line, the photochemical reaction for solving existing polyurethane generate arylamine and then are converted into the life of quinoid or azo structure
Color group, the problem of leading to xanthochromia.
Existing polyurethane synthesis includes mainly polyether-type, polyester-type two major classes, its structure with oligomer polyol (polyol)
The soft segment of the polyurethane of generating polyurethane, usually between 500~3000, different polyglycols is prepared molecular weight with diisocyanate
PU performances it is different；Generally speaking, there are cementability-water imbibition-mechanical properties can not and excellent ask for existing adhesive for polyurethane
Topic.Small molecular alcohol is added as chain extender in the prior art, but the general very little of dosage, avoids precondensation stage gel, prevents from influencing
Polyurethane performance, present invention overcomes prior art prejudice, in the presence of second step polyvinyl alcohol, two isocyanide of hexa-methylene
Acid esters, the pre-reaction of 1,3,5- three-glycidyl-S- triazinetriones and glycerine, third walk several monomers especially cyanate ring
Reaction in the presence of oxygen respectively obtains two kinds of systems, then limits each raw material dosage, after the mixing of the 4th step, carries out polymerisation,
And system rigidity and moisture-proof are adjusted by the addition of ammonium thiocyanate, maleic anhydride, the adhesive for polyurethane obtained from applies
Cover stablize, good weatherability, using pre- poly- solidification is cooperateed with, not only adhesive property is good, and the product after curing is existing heat-resisting good hard
Section, and the soft segment for having flexibility good, and modified complex metal compound mating reaction, in the base of enhancing adhesion strength, water resistance
On plinth, adhesive toughness is fabulous, and excellent in flame retardance.
Specific implementation mode
Embodiment one
A kind of preparation method of no-solvent polyurethane adhesive used for textiles, includes the following steps：
(1) under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol and propionic acid are mixed；It is then refluxed for
Then the ammonium hydroxide that mass concentration is 20% is added in stirring 50 minutes；Back flow reaction 40 minutes；Then revolving removes solvent and is consolidated
Body object；Solids is sintered 10 minutes in 500 DEG C, is then calcined 15 minutes in 650 DEG C, 2000 mesh sieve is crossed after grinding, is taken under sieve
Object be washed to washing after aqueous solution in not chloride ion-containing re-dry obtain functional stuffing；
(2) polyvinyl alcohol (average molecular weight of polyvinyl alcohol is 4800) aqueous solution of mixing quality a concentration of 10%, four
Phenyl PORPHYRIN IRON, peroxidized t-butyl perbenzoate, 80 DEG C are stirred 3 hours, and then revolving removing water, is then added hexa-methylene two
Isocyanates, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 minutes add glycerine, stir to get modification
System；
(3) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, and 2- sulfydryls are then added
Pyridine, hexamethyl trien, 60 DEG C of stirrings add bisphenol A cyanate monomer for 1 hour and phthalic acid two contracts
Water glyceride, hexamethylene diisocyanate, 110 DEG C are stirred 15 minutes, and foundational system is obtained；
(4) functional stuffing is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stir 35 points
Clock adds foundational system, and 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
In the present embodiment, in step (1), six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol, propionic acid, ammonium hydroxide matter
Amount is than being 35: 55: 10: 100: 30: 20；In step (2), polyvinyl alcohol water solution, tetraphenylporphyrin iron, perbenzoic acid uncle
Butyl ester, hexamethylene diisocyanate, 1,3,5- three-glycidyl-S- triazinetriones, glycerine mass ratio be 100: 0.05:
2∶60∶30∶60；In step (3), diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 2- mercaptopyridines, hexamethyl triethylene
Tetramine, bisphenol A cyanate monomer, o-phthalic acid diglycidyl ester, hexamethylene diisocyanate mass ratio be 100:
25∶30∶8∶30∶20∶60∶60；In step (4), functional stuffing, modified system, ammonium thiocyanate, maleic anhydride, foundational system
Mass ratio is 5: 35: 3: 10: 100.
Embodiment two
A kind of preparation method of no-solvent polyurethane adhesive used for textiles, includes the following steps：
(1) under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol and propionic acid are mixed；It is then refluxed for
Then the ammonium hydroxide that mass concentration is 20% is added in stirring 50 minutes；Back flow reaction 40 minutes；Then revolving removes solvent and is consolidated
Body object；Solids is sintered 10 minutes in 500 DEG C, is then calcined 15 minutes in 650 DEG C, 2000 mesh sieve is crossed after grinding, is taken under sieve
Object be washed to washing after aqueous solution in not chloride ion-containing re-dry obtain functional stuffing；
(2) polyvinyl alcohol (average molecular weight of polyvinyl alcohol is 4200) aqueous solution of mixing quality a concentration of 10%, four
Phenyl PORPHYRIN IRON, peroxidized t-butyl perbenzoate, 80 DEG C are stirred 3 hours, and then revolving removing water, is then added hexa-methylene two
Isocyanates, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 minutes add glycerine, stir to get modification
System；
(3) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, and 2- sulfydryls are then added
Pyridine, hexamethyl trien, 60 DEG C of stirrings add bisphenol A cyanate monomer for 1 hour and phthalic acid two contracts
Water glyceride, hexamethylene diisocyanate, 110 DEG C are stirred 15 minutes, and foundational system is obtained；
(4) functional stuffing is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stir 35 points
Clock adds foundational system, and 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
In the present embodiment, in step (1), six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol, propionic acid, ammonium hydroxide matter
Amount is than being 35: 55: 10: 100: 30: 20；In step (2), polyvinyl alcohol water solution, tetraphenylporphyrin iron, perbenzoic acid uncle
Butyl ester, hexamethylene diisocyanate, 1,3,5- three-glycidyl-S- triazinetriones, glycerine mass ratio be 100: 0.05:
2∶60∶30∶60；In step (3), diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 2- mercaptopyridines, hexamethyl triethylene
Tetramine, bisphenol A cyanate monomer, o-phthalic acid diglycidyl ester, hexamethylene diisocyanate mass ratio be 100:
25∶30∶8∶30∶20∶60∶60；In step (4), functional stuffing, modified system, ammonium thiocyanate, maleic anhydride, foundational system
Mass ratio is 5: 35: 3: 10: 100.
Embodiment three
A kind of preparation method of no-solvent polyurethane adhesive used for textiles, includes the following steps：
(1) under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol and propionic acid are mixed；It is then refluxed for
Then the ammonium hydroxide that mass concentration is 20% is added in stirring 50 minutes；Back flow reaction 40 minutes；Then revolving removes solvent and is consolidated
Body object；Solids is sintered 10 minutes in 500 DEG C, is then calcined 15 minutes in 650 DEG C, 2000 mesh sieve is crossed after grinding, is taken under sieve
Object be washed to washing after aqueous solution in not chloride ion-containing re-dry obtain functional stuffing；
(2) polyvinyl alcohol (average molecular weight of polyvinyl alcohol is 4800) aqueous solution of mixing quality a concentration of 10%, four
Phenyl PORPHYRIN IRON, peroxidized t-butyl perbenzoate, 80 DEG C are stirred 3 hours, and then revolving removing water, is then added hexa-methylene two
Isocyanates, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 minutes add glycerine, stir to get modification
System；
(3) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, and 2- sulfydryls are then added
Pyridine, hexamethyl trien, 60 DEG C of stirrings add bisphenol A cyanate monomer for 1 hour and phthalic acid two contracts
Water glyceride, hexamethylene diisocyanate, 110 DEG C are stirred 15 minutes, and foundational system is obtained；
(4) functional stuffing is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stir 35 points
Clock adds foundational system, and 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
In the present embodiment, in step (1), six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol, propionic acid, ammonium hydroxide matter
Amount is than being 35: 55: 10: 100: 30: 20；In step (2), polyvinyl alcohol water solution, tetraphenylporphyrin iron, perbenzoic acid uncle
Butyl ester, hexamethylene diisocyanate, 1,3,5- three-glycidyl-S- triazinetriones, glycerine mass ratio be 100: 0.05:
2∶60∶30∶60；In step (3), diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 2- mercaptopyridines, hexamethyl triethylene
Tetramine, bisphenol A cyanate monomer, o-phthalic acid diglycidyl ester, hexamethylene diisocyanate mass ratio be 100:
25∶30∶8∶30∶20∶60∶60；In step (4), functional stuffing, modified system, ammonium thiocyanate, maleic anhydride, foundational system
Mass ratio is 5: 35: 3: 10: 100.
Comparative example one
A kind of preparation method of no-solvent polyurethane adhesive used for textiles, includes the following steps：
(1) polyvinyl alcohol (average molecular weight of polyvinyl alcohol is 4800) aqueous solution of mixing quality a concentration of 10%, four
Phenyl PORPHYRIN IRON, peroxidized t-butyl perbenzoate, 80 DEG C are stirred 3 hours, and then revolving removing water, is then added hexa-methylene two
Isocyanates, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 minutes add glycerine, stir to get modification
System；
(2) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, and 2- sulfydryls are then added
Pyridine, hexamethyl trien, 60 DEG C of stirrings add bisphenol A cyanate monomer for 1 hour and phthalic acid two contracts
Water glyceride, hexamethylene diisocyanate, 110 DEG C are stirred 15 minutes, and foundational system is obtained；
(3) zinc oxide is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stir 35 minutes
Foundational system is added, 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
In this comparative example, polyvinyl alcohol water solution, tetraphenylporphyrin iron, peroxidized t-butyl perbenzoate, hexa-methylene two
Isocyanates, 1,3,5- three-glycidyl-S- triazinetriones, glycerine mass ratio be 100: 0.05: 2: 60: 30: 60；Two
Glycol, anacardol, N-Methyl pyrrolidone, 2- mercaptopyridines, hexamethyl trien, bisphenol A cyanate monomer, adjacent benzene
Dicarboxylic acid diglycidyl ester, hexamethylene diisocyanate mass ratio be 100: 25: 30: 8: 30: 20: 60: 60；Oxidation
Zinc, modified system, ammonium thiocyanate, maleic anhydride, foundational system mass ratio be 5: 35: 3: 10: 100.
Comparative example two
A kind of preparation method of no-solvent polyurethane adhesive used for textiles, includes the following steps：
(1) under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol and propionic acid are mixed；It is then refluxed for
Then the ammonium hydroxide that mass concentration is 20% is added in stirring 50 minutes；Back flow reaction 40 minutes；Then revolving removes solvent and is consolidated
Body object；Solids is sintered 10 minutes in 500 DEG C, is then calcined 15 minutes in 650 DEG C, 2000 mesh sieve is crossed after grinding, is taken under sieve
Object be washed to washing after aqueous solution in not chloride ion-containing re-dry obtain functional stuffing；
(2) polyvinyl alcohol (average molecular weight of polyvinyl alcohol is 4800) aqueous solution of mixing quality a concentration of 10%, four
Phenyl PORPHYRIN IRON, peroxidized t-butyl perbenzoate, 80 DEG C are stirred 3 hours, and then revolving removing water, is then added hexa-methylene two
Isocyanates, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 minutes add glycerine, stir to get modification
System；
(3) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, and 2- sulfydryls are then added
Pyridine, 60 DEG C of stirrings add o-phthalic acid diglycidyl ester, hexamethylene diisocyanate, 110 DEG C of stirrings 15 for 1 hour
Minute, obtain foundational system；
(4) functional stuffing is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stir 35 points
Clock adds foundational system, and 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
In this comparative example, in step (1), six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol, propionic acid, ammonium hydroxide matter
Amount is than being 35: 55: 10: 100: 30: 20；In step (2), polyvinyl alcohol water solution, tetraphenylporphyrin iron, perbenzoic acid uncle
Butyl ester, hexamethylene diisocyanate, 1,3,5- three-glycidyl-S- triazinetriones, glycerine mass ratio be 100: 0.05:
2∶60∶30∶60；In step (3), diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 2- mercaptopyridines, phthalic acid two contract
Water glyceride, hexamethylene diisocyanate mass ratio be 100: 15: 30: 10: 50: 80；In step (4), functional stuffing,
Modified system, ammonium thiocyanate, maleic anhydride, foundational system mass ratio be 5: 35: 3: 10: 100.
Comparative example three
A kind of preparation method of no-solvent polyurethane adhesive used for textiles, includes the following steps：
(1) under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol and propionic acid are mixed；It is then refluxed for
Then the ammonium hydroxide that mass concentration is 20% is added in stirring 50 minutes；Back flow reaction 40 minutes；Then revolving removes solvent and is consolidated
Body object；Solids is sintered 10 minutes in 500 DEG C, is then calcined 15 minutes in 650 DEG C, 2000 mesh sieve is crossed after grinding, is taken under sieve
Object be washed to washing after aqueous solution in not chloride ion-containing re-dry obtain functional stuffing；
(2) polyvinyl alcohol (average molecular weight of polyvinyl alcohol is 4800) aqueous solution of mixing quality a concentration of 10%, four
Phenyl PORPHYRIN IRON, peroxidized t-butyl perbenzoate, 80 DEG C are stirred 3 hours, and then revolving removing water, is then added hexa-methylene two
Isocyanates, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 minutes add glycerine, stir to get modification
System；
(3) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, and hexamethyl is then added
Trien, 60 DEG C of stirrings add bisphenol A cyanate monomer and o-phthalic acid diglycidyl ester, six in 1 hour
Methylene diisocyanate, 110 DEG C are stirred 15 minutes, and foundational system is obtained；
(4) functional stuffing is added in modified system, 60 DEG C of stirrings add foundational system, 110 DEG C of stirrings 85 for 35 minutes
Minute, Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
In this comparative example, in step (1), six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol, propionic acid, ammonium hydroxide matter
Amount is than being 35: 55: 10: 100: 30: 20；In step (2), polyvinyl alcohol water solution, tetraphenylporphyrin iron, perbenzoic acid uncle
Butyl ester, hexamethylene diisocyanate, 1,3,5- three-glycidyl-S- triazinetriones, glycerine mass ratio be 100: 0.05:
2∶60∶30∶60；In step (3), diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, methylene diisocyanate mass ratio be
100∶15∶30∶30∶20∶50∶80；In step (4), functional stuffing, modified system, foundational system mass ratio be 5: 35: 100.
Viscosity, the gluing of embodiment one are evaluated with reference to GB/T2790-1995 adhesive 180 degree peeling strength test method
The peel strength of agent is 220N/ (2.5cm), and the peel strength of the adhesive of embodiment two is 223N/ (2.5cm), embodiment three
The peel strength of adhesive be 215N/ (2.5cm), the peel strength of the adhesive of comparative example one is 181N/ (2.5cm), right
The peel strength of the adhesive of ratio two is 170N/ (2.5cm), and the peel strength of the adhesive of comparative example three is 202N/
(2.5cm)；Embodiment product is placed 30 days at 60 DEG C, and peel strength hardly changes.
The measurement (each taking five samples, each sample test three times, be averaged) of water resistance, by above-mentioned polyurethane adhesive
Glutinous agent is coated in release paper, is dried at 40 DEG C and is obtained within 2 hours glued membrane, after precise, is immersed in deionized water, is taken afterwards for 24 hours
Go out, suck the free moisture in surface, water absorption rate is calculated according to weight change；The rate of drying of the adhesive for polyurethane of the present invention
Height, embodiment one, embodiment two, the water absorption rate of embodiment three for 24 hours are 0.95%, 1.02%, 0.99%, and glued membrane is not sent out
In vain, water resistance is good；Comparative example one, comparative example two, the water absorption rate of comparative example three for 24 hours are 2.68%, 3.98%, 2.42%, glue
Film, which is not apparent from, to whiten；And embodiment sample bend 5000 times it is not broken, toughness is extremely strong.
Test ultraviolet xanthochromia performance under 500KWh, embodiment one, embodiment two, embodiment three △ b be respectively 0.52,
0.49,0.53, comparative example one, comparative example two, comparative example three △ b be respectively 2.99,0.65,0.98；The present invention, which limits, to be prepared
Obtained adhesive thermal stress suffered in preparation process substantially reduces, and has delayed adhesive during accelerated hydrothermal aging
Destruction process.
Flame retardant property reference GB 12441-2005, the mass loss of embodiment one, embodiment two, embodiment three are respectively
1.03g, 1.08g, 1.05g, the mass loss of comparative example one, comparative example two, comparative example three be respectively 3.68g, 1.98g,
2.32g；Embodiment one, embodiment two, embodiment three char volume be respectively 0.84cm3、0.85cm3、0.85cm3, comparison
Example one, comparative example two, comparative example three char volume be respectively 1.64cm3、1.12cm3、1.05cm3。
Claims (10)
1. a kind of preparation method of no-solvent polyurethane adhesive used for textiles, which is characterized in that include the following steps：
(1) under nitrogen protection, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol and propionic acid are mixed；It is then refluxed for stirring
50 minutes, ammonium hydroxide is then added；Back flow reaction 40 minutes；Then it removes solvent and obtains solids；By solids in 500 DEG C of sintering
It 10 minutes, is then calcined 15 minutes in 650 DEG C, grinds, washes, is dried to obtain functional stuffing；
(2) mix polyethylene alcohol solution, tetraphenylporphyrin iron, peroxidized t-butyl perbenzoate, 80 DEG C stir 3 hours, then
Water is removed, then addition hexamethylene diisocyanate, 1,3,5- three-glycidyl-S- triazinetriones, return stirring 5 minutes,
Glycerine is added, modified system is stirred to get；
(3) after mixing diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 60 DEG C are stirred 1 hour, be then added 2- mercaptopyridines,
Hexamethyl trien, 60 DEG C of stirrings add bisphenol A cyanate monomer and phthalic acid 2-glycidyl in 1 hour
Ester, hexamethylene diisocyanate, 110 DEG C are stirred 15 minutes, and foundational system is obtained；
(4) functional stuffing is added in modified system, 60 DEG C are added with stirring ammonium thiocyanate, maleic anhydride, stir 35 minutes again
Foundational system is added, 110 DEG C are stirred 85 minutes, and Temperature fall obtains no-solvent polyurethane adhesive used for textiles.
2. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that the ammonia
Water quality a concentration of 20%；The mass concentration of the polyvinyl alcohol water solution is 10%.
3. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that step
(1) 2000 mesh sieve is crossed in, after grinding, extracting screen underflow washing is dried to obtain functional stuffing.
4. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that step
(1) in, solvent is removed using revolving method, is washed in the aqueous solution after washing not chloride ion-containing.
5. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that step
(1) in, six ammonium chloroiridates, nitric hydrate nickel, cobalt nitrate, ethyl alcohol, propionic acid, ammonium hydroxide mass ratio be 35: 55: 10: 100: 30:
20。
6. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that step
(2) in, the average molecular weight of polyvinyl alcohol is 4000~5000.
7. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that step
(2) in, polyvinyl alcohol water solution, tetraphenylporphyrin iron, peroxidized t-butyl perbenzoate, hexamethylene diisocyanate, 1,3,
5- three-glycidyl-S- triazinetriones, glycerine mass ratio be 100: 0.05: 2: 60: 30: 60.
8. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that step
(3) in, diethylene glycol (DEG), anacardol, N-Methyl pyrrolidone, 2- mercaptopyridines, hexamethyl trien, bisphenol A cyanate
Monomer, o-phthalic acid diglycidyl ester, hexamethylene diisocyanate mass ratio be 100: 25: 30: 8: 30: 20: 60:
60。
9. the preparation method of no-solvent polyurethane adhesive used for textiles according to claim 1, which is characterized in that step
(4) in, functional stuffing, modified system, ammonium thiocyanate, maleic anhydride, foundational system mass ratio be 5: 35: 3: 10: 100.
10. the polyurethane gluing that according to claim 1 prepared by the preparation method of no-solvent polyurethane adhesive used for textiles
Agent.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255433A (en) * | 2015-11-17 | 2016-01-20 | 湖北回天新材料股份有限公司 | One-component moisture cured polyurethane sealant excellent in weather resistance and preparation method thereof |
| CN107118516A (en) * | 2017-06-20 | 2017-09-01 | 苏州大学 | A kind of non-dusting brush and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105255433A (en) * | 2015-11-17 | 2016-01-20 | 湖北回天新材料股份有限公司 | One-component moisture cured polyurethane sealant excellent in weather resistance and preparation method thereof |
| CN107118516A (en) * | 2017-06-20 | 2017-09-01 | 苏州大学 | A kind of non-dusting brush and preparation method thereof |
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