CN106520053A - High-performance adhesive and its preparation method and use - Google Patents
High-performance adhesive and its preparation method and use Download PDFInfo
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- CN106520053A CN106520053A CN201610992292.0A CN201610992292A CN106520053A CN 106520053 A CN106520053 A CN 106520053A CN 201610992292 A CN201610992292 A CN 201610992292A CN 106520053 A CN106520053 A CN 106520053A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a high-performance adhesive. The high-performance adhesive comprises polyester diol, diisocyanate and a chain extender according to a mass ratio of 1: 0.42: 0.25 to 1: 0.85: 0.85. The high-performance adhesive has the advantages of use of easily available raw materials, curing at the room temperature or under heating, no side reaction, operation simpleness and strong adhesion.
Description
Technical field
The invention belongs to a kind of High-performance adhesive and preparation method and application.
Background technology
Adhesive for polyurethane arises from nineteen forties, and polyurethane (PU) is general by isocyanates, polyhydric alcohol, chain extension
The composition such as agent and other additives, due to containing the polarized very active isocyanates of strong, chemical and urethano, can be with active hydrogen
Reaction, forms excellent chemical adhesive power；Simultaneously adhesive for polyurethane has excellent lower temperature resistance, with good wearability,
The performances such as resistance to water, solvent resistance, the chemically-resistant property of medicine, its good adhesive property to metal, rubber, glass, ceramics, plastics,
The multiple materials such as timber, plant, leather have stronger bonding adaptability, so as to be widely used in many fields.Polyurethane
Adhesive is divided into three major types according to reaction composition：Polyisocyanates gluing agent, base polyurethane prepolymer for use as adhesive, polyurethane resin adhesive
Glutinous agent.
As market increases to the demand of adhesive, performance requirement is higher, and the adhesive of single molecule can not be expired completely
Sufficient use requirement, it is therefore necessary to be modified to which, method of modifying have physical modification and chemical modification.Physical modification is exactly to pass through
The method of physics blending adds other materials in adhesive for polyurethane, improves the performance of adhesive, such as adds silica flour, nanometer
Material etc..Chemical modification refers to and high performance polymer or group introduced in polyurethane backbone or side chain, such as silicon atom,
Hiroshi such as sulphur atom, epoxy radicals, naphthalene ring et al. adopt 4,4 '-dimercapto biphenyl (BPT), 4,4 '-glycol biphenyl
(BPH) a series of sulfur-bearing linear polyesters and not sulfur-bearing polyester are synthesized, result finds sulfur-bearing linear polyester not only table after contrast
Existing thermotropic liquid crystal behavior, and adhesive property is more much higher than not sulfur-bearing polyester, and this is caused from the different of ester bond due to thioester bond
's.
Kultys mentions aromatic series sulfone in Kirk-Othmer chemical technology encyclopaedias and birdss of the same feather flock together compound due to sulfone on main chain
The presence of ester group, with good physical chemistry, electrical property, hot property and processability, good adhesive property makes which also may be used
Use as adhesive.
According to report, the introducing of element sulphur is conducive to the adhesive property for improving polymer, and polyurethane is general more with chemistry
Method is modified, and can change the structure of polyurethane from basic composition.By synthesizing sulfur-bearing diol chain-extension agent, tie in polyurethane backbone
The research that the adhesive property that element sulphur improves polyurethane is introduced in structure has not been reported.
The content of the invention
The present invention provides a kind of synthetic method that polyurethane adhesive performance is improved by sulfur-bearing chain extender, easy with raw material
, can room temperature or be heating and curing, without side reaction, simple to operate, cementability is strong the features such as.
The adhesive of the present invention includes polyester-diol, diisocyanate and chain extender, polyester-diol, diisocyanate and expansion
The mass ratio of chain agent is 1:0.42:0.25-1:0.85:0.85, preferably 1:0.51:0.66-1:0.54:0.70.
Synthetic method of the present invention, comprises the steps：
(1) synthesis of sulfur-bearing chain extender
In the reactor, concentration is added to be 10wt%-30wt%NaOH aqueous solutions and mercaptan, by chlorhydrin and dehydrated alcohol
It is added dropwise in system under vigorous stirring after mix homogeneously, 60-90 DEG C is warming up to after Deca 5-10min, insulation reaction 1-
3h, reaction are cooled to room temperature after terminating, and with distillation washing 2-4 time after vacuum filtration, obtain crude product, carried with benzene after being dried afterwards
It is pure 2-4 time, powder solid is obtained after vacuum drying；
(2) synthesis of adhesive
By polyester-diol at 100-120 DEG C vacuum dehydration 1-3h；The polyester-diol being dehydrated is added in reactor,
Diisocyanate is added after 40-50 DEG C is heated under stirring, reaction temperature 80-90 DEG C is warming up to and during insulation reaction 2-3h is obtained
Mesosome, reaction terminate rear vacuum outgass 0.5-1h, are incubated 80-100 DEG C of intermediate and seal standby；Sulfur-bearing chain extender need to be used and added
Hot jacket melts (80-100 DEG C), takes appropriate intermediate and mixes in 80-100 DEG C of quick stirring with the sulfur-bearing chain extender of fusing, reacts
After obtain adhesive.
In the synthesis of sulfur-bearing chain extender as described in (1st) step, mercaptan functionality used is 2, including 1,3- dimercaptopropanes,
1,4- succinimide mercaptans, 1,5- pentane disulfide thioalcohols, 1,6- ethanthiols, 2- phenyl -1,3- dimercaptopropanes, 1,4- benzene dimethanethiols, 1,
4- benzenethiols, biphenyl -4,4 '-mercaptan, 4,4 '-dimercapto diphenyl sulfide, preferably 4,4 '-dimercapto diphenyl sulfide, Isosorbide-5-Nitrae-benzene two
Methanthiol.Element sulphur is introduced by chain extender in polyurethane structural, the cementability between PU and base material can be improved.
In the synthesis of sulfur-bearing chain extender as described in (1st) step, chlorhydrin used includes the chloro- 1- of the chloro- 1- ethanol of 2-, 3- third
The chloro- 1- amylalcohols of the chloro- n-butyl alcohol of alcohol, 4-, 5-, the chloro- 1- hexanols of 6- etc., the chloro- 1- hexanols of preferred trimethylene chlorohydrin, 6-.
In the synthesis of sulfur-bearing chain extender as described in (1st) step, aqueous solution NaOH concentration is 10wt%-30wt%, preferably
10wt%-20wt%；NaOH：Mercaptan：The mol ratio of chlorhydrin is 2.0:1:2.0-5.5:1:2.2, preferably 4.2:1:2.10-
5.5:1:2.2；Chlorhydrin is 1 with dehydrated alcohol mol ratio:1-1:2.5, preferably 1:2.0-1:2.5.
Time for adding 5-10min in the synthesis of sulfur-bearing chain extender as described in (1st) step, reaction temperature are 60-90 DEG C, reaction
Time 1-3h, preferred time for adding 7-10min, reaction temperature 85-90 DEG C, response time 2.5-3h.
Polyester-diol as described in (2nd) step includes 10PE27, poly adipate succinic acid ester, polyadipate
Ethylene glycol and 1,2-propylene glycol ester, polyadipate ethylene glycol-butanediol ester, polyadipate hexanediol ester, polyadipate ethylene glycol-new penta
Diol ester, poly-epsilon-caprolactone glycol, PCDL etc., and polyester-diol molecular weight ranges are 700-2000.It is preferred that gathering oneself
Succinate adipate (PBA), poly-epsilon-caprolactone glycol (PCL), preferred molecular weight is 1000-2000.
Diisocyanate as described in (2nd) step includes toluene di-isocyanate(TDI) (TDI), 4,4 '-diphenyl methane two is different
Cyanate (MDI), PPDI (PPDI), 1,5- naphthalene diisocyanate (NDI), 1, hexamethylene-diisocyanate (HDI),
Isophorone diisocyanate (IPDI) etc., preferred MDI.
During adhesive as described in (2nd) step is prepared, polyester-diol is 80-90 DEG C with di-isocyanate reaction temperature, instead
It is 2-3h between seasonable.Preferable reaction temperature is 85-90 DEG C, and the response time is 2.5-3h.
During adhesive as described in (2nd) step is prepared, the mass ratio of polyester-diol, diisocyanate and chain extender is 1:
0.42:0.25-1:0.85:0.85, preferably 1:0.51:0.66-1:0.54:0.70.
During adhesive as described in (2nd) step is prepared, sulfur-bearing chain extender used need to be melted with heating mantle, it is ensured that chain extender
Shape and the melt temperature range of being in a liquid state before the use is 80-100 DEG C；Intermediate temperature used is 80-100 DEG C.
The application of adhesive of the present invention, comprises the steps：
(1) weak interface layer is removed, is dried in 60-70 DEG C to remove the impurity such as surface grease with solvent wiping substrate surface
It is standby afterwards；
(2) adhesive is picked with Glass rod, be equably applied to substrate surface, after placing 10-25min, by two plate substrates
Smear place to overlap, after 60-70 DEG C of baking oven 20-30h is put under pressure 3500-4000Pa, take out to be measured.
Base material includes plastics, rubber, leather, timber etc., preferred plastics, such as polrvinyl chloride (PVC) as mentioned above.
Base material treatment solvent for use includes acetone, butanone, ethyl acetate, dimethylformamide, dimethyl second as mentioned above
Amide, tetrahydrofuran etc., preferred acetone.
The drying temperature of base material processed as above is preferred 65-70 DEG C.
The amount of adhesive used by base material is 0.15-0.35g/cm as mentioned above2, preferred 0.25-0.3g/cm2。
As described above, it is preferred to standing time 20-25min, pressure 3800-4000Pa, place temperature 65-70 DEG C, during placement
Between 24-30h.
The present invention is had the advantage that compared with prior art：
1st, raw material is easy to get, and technique for sticking is simple to operate, and mucosa hardness has adjustability；
2nd, the synthetic reaction of chain extender is easy to control, and yield is high, purity height (>=99.5%)；
3rd, compare with not sulfur-bearing chain extender, by using sulfur-bearing chain extender, element sulphur is introduced in polyurethane structural, can be carried
The adhesive strength of high polyurethane is up to 170.95%；
4th, the solventless adhesive for preparing, containing highly polar carbamate groups, with very high reactivity, low
Poison ring is protected, and room temperature or heating are all curable, and performance adjustable extent is larger, and bonding force is strong, to plastics, rubber, leather, timber
Deng the stronger bonding adaptability of multiple material.
Specific embodiment
Below embodiments of the invention are elaborated：Embodiment carries out reality on the premise of technical solution of the present invention
Apply, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
In following each embodiments, used polyester-diol is need to be in 120 DEG C and -0.09～-0.095MPa vacuum using before
The lower dehydration of degree 3 hours, then sealing preserve is standby.Used sulfur-bearing diol chain-extension agent is dried in vacuum drying oven 3 hours, is made
Melted with heating is needed before.
In following each embodiments, used polyester-diol, diisocyanate and chain extender are being heated respectively using front,
Need to be in a liquid state shape.
Performance test in following examples：Its cementability is tested after one week being placed under the sample strip room temperature of preparation
Can, adhesive property tests its T- peel strength by GB GB/T2791-1995.
Comparative example 1
First step chain extender is anticipated
By chain extender BDO at 100 DEG C vacuum dehydration 2h, seal it is standby；
The synthesis of second step adhesive
(1) by poly adipate succinic acid ester (molecular weight is 1000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) poly adipate succinic acid ester being dehydrated (100g) is added in reactor, after being heated to 45 DEG C under agitation
MDI (64g) is added, 85 DEG C and insulation reaction 2.5h is warming up to, reaction terminates rear vacuum outgass 0.5h, seal intermediate afterwards standby
With.
(3) adhesive is prepared：Take the intermediate (10g, 85 DEG C) described in (2), and chain extender BDO (0.81g, 45
DEG C), then both are mixed and are quickly stirred, obtain adhesive.
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, wipes its surface to remove with acetone
The impurity such as surface grease, remove weak interface layer, are put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (4g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 20min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 65 DEG C of baking oven 24h under pressure 4000Pa.Room temperature is peeled off strong after placing one week
Spend for 60.25N 2.5cm-1。
Comparative example 2
First step chain extender is anticipated
By chain extender BDO at 100 DEG C vacuum dehydration 2h, seal it is standby；
The synthesis of second step adhesive
(1) by poly-epsilon-caprolactone glycol (molecular weight is 1000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) the poly-epsilon-caprolactone glycol (100g) being dehydrated is added in reactor, is added after being heated to 45 DEG C under agitation
Enter MDI (64g), be warming up to 90 DEG C and insulation reaction 3h, reaction terminates rear vacuum outgass 0.5h, seal intermediate afterwards standby.
(3) adhesive is prepared：Take the intermediate (10g, 90 DEG C) described in (2), and chain extender BDO (0.81g, 50
DEG C), then both are mixed and are quickly stirred, obtain adhesive.
The application of the 3rd step adhesive
(1) using chemical method process PVC pieces (100mm × 25mm × 1mm) surface, with tetrahydrofuran wipe its surface with
The impurity such as surface grease are removed, weak interface layer is removed, is put into standby after 70 DEG C of baking oven 20min are dried.
(2) adhesive (5g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 20min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 70 DEG C of baking oven 28h under pressure 4000Pa.Room temperature is peeled off strong after placing one week
Spend for 62N 2.5cm-1。
Embodiment 1
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 10%NaOH aqueous solutions are added
(151.2g) He 4,2- chloro- 1- ethanol (0.2mol) is mixed by 4 '-dimercapto diphenyl sulfide (0.1mol) with 11.7mL dehydrated alcohol
It is added dropwise in system under vigorous stirring after closing uniformly, Deca 5min is warming up to 90 DEG C after finishing, insulation reaction 1h.Reaction
Room temperature is cooled to after end, after vacuum filtration, crude product is dried to obtain twice with distillation washing, purified twice with benzene afterwards, vacuum
Powder solid is obtained after drying, yield 68.77% is sealed standby.
The synthesis of second step adhesive
(1) by 10PE27 (molecular weight is 1000) the vacuum dehydration 3h at 100 DEG C, seal standby；
(2) 10PE27 being dehydrated (100g) is added in reactor, after being heated to 45 DEG C under agitation
MDI (57.89g) is added, 80 DEG C and insulation reaction 3h is warming up to, reaction terminates rear vacuum outgass 0.5h, seals intermediate afterwards
It is standby.
(3) adhesive is prepared：Take the intermediate (10g, 80 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.68g, 100 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, wipes its surface to remove with acetone
The impurity such as surface grease, remove weak interface layer, are put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (3g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 20min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 70 DEG C of baking oven 24h under pressure 3800Pa.Room temperature is peeled off strong after placing one week
Spend for 64.92N 2.5cm-1, compare with comparative example 1 and improve 7.75%.
Embodiment 2
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 15%NaOH aqueous solutions are added
(100.8g) He 1,3- dimercaptopropane (0.1mol), trimethylene chlorohydrin (0.21mol) is mixed homogeneously with 24.5mL dehydrated alcohol
It is added dropwise under vigorous stirring in system afterwards, Deca 6min is warming up to 85 DEG C after finishing, insulation reaction 1.5h.Reaction terminates
After be cooled to room temperature, after vacuum filtration with distillation washing be dried to obtain crude product twice, afterwards with benzene purify twice, vacuum drying
After obtain powder solid, yield 72.04% is sealed standby.
The synthesis of second step adhesive
(1) by poly adipate succinic acid ester (molecular weight is 700) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) poly adipate succinic acid ester being dehydrated (100g) is added in reactor, after being heated to 45 DEG C under agitation
MDI (74.71g) is added, 90 DEG C and insulation reaction 2h is warming up to, reaction terminates rear vacuum outgass 0.5h, seals intermediate afterwards
It is standby.
(3) adhesive is prepared：Take the intermediate (10g, 85 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (1.90g, 80 DEG C).
The application of the 3rd step adhesive
(1) using chemical method process rubber sample (100mm × 25mm × 1mm) surface, with butanone wipe its surface with
The impurity such as surface grease are removed, weak interface layer is removed, is put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (3g) of (3) is picked with Glass rod, rubber sample surface is equably applied to.After placing 20min,
The two panels rubber sample place of smearing is overlapped, is put under pressure 3800Pa to be tested after 70 DEG C of baking oven 30h.After room temperature is placed one week
Peel strength is 68.54N 2.5cm-1, compare with comparative example 1 and improve 13.76%.
Embodiment 3
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 10%NaOH aqueous solutions are added
(100.8g) He 1,6- ethanthiol (0.1mol), 4- chloro- n-butyl alcohol (0.21mol) is mixed homogeneously with 30.6mL dehydrated alcohol
It is added dropwise under vigorous stirring in system afterwards, Deca 7min is warming up to 90 DEG C after finishing, insulation reaction 1.5h.Reaction terminates
After be cooled to room temperature, after vacuum filtration with distillation washing be dried to obtain crude product twice, afterwards with benzene purify twice, vacuum drying
After obtain powder solid, yield 72.58% is sealed standby.
The synthesis of second step adhesive
(1) by polyadipate ethylene glycol and 1,2-propylene glycol ester (molecular weight is 1500) the vacuum dehydration 3h at 120 DEG C, seal standby
With；
(2) polyadipate ethylene glycol and 1,2-propylene glycol ester (100g) being dehydrated is added in reactor, is heated under agitation
MDI (53.12g) is added after 45 DEG C, 84 DEG C and insulation reaction 3h is warming up to, reaction terminates rear vacuum outgass 0.5h, seals afterwards
Intermediate is standby.
(3) adhesive is prepared：Take the intermediate (10g, 90 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.40g, 85 DEG C).
The application of the 3rd step adhesive
(1) wood pieces (100mm × 25mm × 1mm) surface is processed using chemical method, its table is wiped with tetrahydrofuran
Face removes weak interface layer to remove the impurity such as surface grease, is put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (4g) of (3) is picked with Glass rod, wood sample surface is equably applied to.After placing 21min,
The two panels wood sample place of smearing is overlapped, is put under pressure 3800Pa to be tested after 70 DEG C of baking oven 24h.After room temperature is placed one week
Peel strength is 70.75N 2.5cm-1, compare with comparative example 1 and improve 17.43%.
Embodiment 4
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 20%NaOH aqueous solutions are added
(60g) with 2- phenyl -1,5- chloro- 1- amylalcohols (0.2mol) are mixed by 3- dimercaptopropanes (0.1mol) with 23.3mL dehydrated alcohol
It is added dropwise in system under vigorous stirring after uniform, Deca 10min is warming up to 60 DEG C after finishing, insulation reaction 3h.Reaction
Room temperature is cooled to after end, after vacuum filtration, crude product is dried to obtain twice with distillation washing, purified twice with benzene afterwards, vacuum
Powder solid is obtained after drying, yield 67.62% is sealed standby.
The synthesis of second step adhesive
(1) by polyadipate ethylene glycol-butanediol ester (molecular weight is 700) the vacuum dehydration 3h at 120 DEG C, seal standby
With；
(2) polyadipate being dehydrated ethylene glycol-butanediol ester (100g) is added in reactor, is heated under agitation
TDI (50.8g) is added after 45 DEG C, 83 DEG C and insulation reaction 3h is warming up to, reaction terminates rear vacuum outgass 0.5h, in sealing afterwards
Mesosome is standby.
(3) adhesive is prepared：Take the intermediate (10g, 95 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.72g, 90 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, its table is wiped with dimethylformamide
Face removes weak interface layer to remove the impurity such as surface grease, is put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (4g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 21min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 70 DEG C of baking oven 24h under pressure 3850Pa.Room temperature is peeled off strong after placing one week
Spend for 68.89N 2.5cm-1, compare with comparative example 1 and improve 14.34%.
Embodiment 5
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 25%NaOH aqueous solutions are added
(50g) He 4,6- chloro- 1- hexanols (0.22mol) are mixed by 4 '-dimercapto diphenyl sulfide (0.1mol) with 29.1mL dehydrated alcohol
It is added dropwise in system under vigorous stirring after uniform, Deca 9min is warming up to 70 DEG C after finishing, insulation reaction 2.5h.Reaction
Room temperature is cooled to after end, after vacuum filtration, crude product is dried to obtain twice with distillation washing, purified twice with benzene afterwards, vacuum
Powder solid is obtained after drying, yield 75.60% is sealed standby.
The synthesis of second step adhesive
(1) by polyadipate hexanediol ester (molecular weight is 2000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) polyadipate hexanediol ester (100g) being dehydrated is added in reactor, after being heated to 45 DEG C under agitation
MDI (64g) is added, 90 DEG C and insulation reaction 2h is warming up to, reaction terminates rear vacuum outgass 0.5h, seal intermediate afterwards standby
With.
(3) adhesive is prepared：Take the intermediate (10g, 100 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (4.07g, 95 DEG C).
The application of the 3rd step adhesive
(1) using chemical method process PVC pieces (100mm × 25mm × 1mm) surface, with ethyl acetate wipe its surface with
The impurity such as surface grease are removed, weak interface layer is removed, is put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (5g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.22min is placed, by two panels
The PVC pieces place of smearing overlaps, and is put into be tested after 67 DEG C of baking oven 28h under pressure 3850Pa.Room temperature place one week after peel strength
For 136.50N 2.5cm-1, compare with comparative example 1 and improve 126.56%.
Embodiment 6
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 30%NaOH aqueous solutions are added
(73.3g) with Isosorbide-5-Nitrae-benzene dimethanethiol (0.1mol), trimethylene chlorohydrin (0.21mol) is mixed with 24.5mL dehydrated alcohol
It is added dropwise in system under vigorous stirring after even, Deca 8min is warming up to 75 DEG C after finishing, insulation reaction 3h.Reaction terminates
After be cooled to room temperature, after vacuum filtration with distillation washing be dried to obtain crude product twice, afterwards with benzene purify twice, vacuum drying
After obtain powder solid, yield 76.91% is sealed standby.
The synthesis of second step adhesive
(1) by polyadipate ethylene glycol-DOPCP (molecular weight is 700) the vacuum dehydration 3h at 120 DEG C, seal standby
With；
(2) polyadipate being dehydrated ethylene glycol-DOPCP (100g) is added in reactor, is heated under agitation
TDI (46.03g) is added to after 45 DEG C, 80 DEG C and insulation reaction 3h is warming up to, reaction terminates rear vacuum outgass 0.5h, Zhi Houmi
Envelope intermediate is standby.
(3) adhesive is prepared：Take the intermediate (10g, 95 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.26g, 90 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, wipes its surface to remove with acetone
The impurity such as surface grease, remove weak interface layer, are put into standby after 66 DEG C of baking oven 10min are dried.
(2) adhesive (4g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 24min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 70 DEG C of baking oven 24h under pressure 3900Pa.Room temperature is peeled off strong after placing one week
Spend for 97.75N 2.5cm-1, compare with comparative example 1 and improve 62.24%.
Embodiment 7
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 10%NaOH aqueous solutions are added
(140g) with Isosorbide-5-Nitrae-benzene dimethanethiol (0.1mol), 6- chloro- 1- hexanols (0.22mol) are mixed homogeneously with 29.1mL dehydrated alcohol
It is added dropwise under vigorous stirring in system afterwards, Deca 10min is warming up to 85 DEG C after finishing, insulation reaction 3h.Reaction terminates
After be cooled to room temperature, after vacuum filtration with distillation washing be dried to obtain crude product twice, afterwards with benzene purify twice, vacuum drying
After obtain powder solid, yield 81.32% is sealed standby.
The synthesis of second step adhesive
(1) by poly adipate succinic acid ester (molecular weight is 2000) the vacuum dehydration 3h at 100 DEG C, seal standby；
(2) poly adipate succinic acid ester being dehydrated (100g) is added in reactor, after being heated to 45 DEG C under agitation
MDI (64g) is added, 85 DEG C and insulation reaction 3h is warming up to, reaction terminates rear vacuum outgass 0.5h, seal intermediate afterwards standby
With.
(3) adhesive is prepared：Take the intermediate (10g, 100 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (3.35g, 95 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, wipes its surface to remove with butanone
The impurity such as surface grease, remove weak interface layer, are put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (5g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 24min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 70 DEG C of baking oven 24h under pressure 3900Pa.Room temperature is peeled off strong after placing one week
Spend for 163.25N 2.5cm-1, compare with comparative example 1 and improve 170.95%.
Embodiment 8
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 15%NaOH aqueous solutions are added
(106.7g) with Isosorbide-5-Nitrae-benzenethiol (0.1mol), after trimethylene chlorohydrin (0.21mol) is mixed homogeneously with 24.5mL dehydrated alcohol
It is added dropwise in system under vigorous stirring, Deca 10min is warming up to 90 DEG C after finishing, insulation reaction 2h.After reaction terminates
Room temperature is cooled to, and crude product is dried to obtain twice with distillation washing after vacuum filtration, is purified twice, after vacuum drying with benzene afterwards
Powder solid is obtained, yield 78.32% is sealed standby.
The synthesis of second step adhesive
(1) by poly-epsilon-caprolactone glycol (molecular weight is 1000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) the poly-epsilon-caprolactone glycol (100g) being dehydrated is added in reactor, is added after being heated to 45 DEG C under agitation
Enter IPDI (54.96g), be warming up to 86 DEG C and insulation reaction 2.5h, reaction terminates rear vacuum outgass 0.5h, seals intermediate afterwards
It is standby.
(3) adhesive is prepared：Take the intermediate (10g, 100 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.33g, 100 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, its table is wiped with dimethyl acetylamide
Face removes weak interface layer to remove the impurity such as surface grease, is put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (4g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 25min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 68 DEG C of baking oven 25h under pressure 3950Pa.Room temperature is peeled off strong after placing one week
Spend for 72.75N 2.5cm-1, compare with comparative example 2 and improve 17.33%.
Embodiment 9
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 10%NaOH aqueous solutions are added
(151.2g) with Isosorbide-5-Nitrae-succinimide mercaptans (0.1mol), 6- chloro- 1- hexanols (0.21mol) are mixed homogeneously with 26.2mL dehydrated alcohol
It is added dropwise under vigorous stirring in system afterwards, Deca 7min is warming up to 90 DEG C after finishing, insulation reaction 2.5h.Reaction terminates
After be cooled to room temperature, after vacuum filtration with distillation washing be dried to obtain crude product twice, afterwards with benzene purify twice, vacuum drying
After obtain powder solid, yield 86.32% is sealed standby.
The synthesis of second step adhesive
(1) by poly-epsilon-caprolactone glycol (molecular weight is 1000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) the poly-epsilon-caprolactone glycol (100g) being dehydrated is added in reactor, is added after being heated to 45 DEG C under agitation
Enter IPDI (54.96g), be warming up to 86 DEG C and insulation reaction 3h, reaction terminates rear vacuum outgass 0.5h, seal intermediate afterwards standby
With.
(3) adhesive is prepared：Take the intermediate (10g, 90 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.15g, 90 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, wipes its surface to remove with acetone
The impurity such as surface grease, remove weak interface layer, are put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (4g) of (3) is picked with Glass rod, after being equably applied to PVC pieces surface placement 25min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 65 DEG C of baking oven 28h under pressure 4000Pa.Room temperature is peeled off strong after placing one week
Spend for 82.00N 2.5cm-1, compare with comparative example 2 and improve 32.25%.
Embodiment 10
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 20%NaOH aqueous solutions are added
(84g) He 1,5- pentane disulfide thioalcohol (0.1mol), after 6- chloro- 1- hexanols (0.2mol) are mixed homogeneously with 17.5mL dehydrated alcohol
It is added dropwise under strong agitation in system, Deca 10min is warming up to 80 DEG C after finishing, insulation reaction 2h.Reaction is cold after terminating
But to room temperature, after vacuum filtration, crude product is dried to obtain twice with distillation washing, purified twice with benzene afterwards, after vacuum drying
To powder solid, yield 76.41%, seal standby.
The synthesis of second step adhesive
(1) by PCDL (molecular weight is 1000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) PCDL being dehydrated (100g) is added in reactor, is added after being heated to 45 DEG C under agitation
MDI (64g), is warming up to 88 DEG C and insulation reaction 2.5h, and reaction terminates rear vacuum outgass 0.5h, seals intermediate afterwards standby.
(3) adhesive is prepared：Take the intermediate (10g, 90 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.30g, 85 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, wipes its surface to remove with butanone
The impurity such as surface grease, remove weak interface layer, are put into standby after 65 DEG C of baking oven 10min are dried.
(2) adhesive (7g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 25min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 70 DEG C of baking oven 25h under pressure 4000Pa.Room temperature is peeled off strong after placing one week
Spend for 77.75N 2.5cm-1, compare with comparative example 2 and improve 25.40%.
Embodiment 11
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 10%NaOH aqueous solutions are added
(84g) with Isosorbide-5-Nitrae-benzene dimethanethiol (0.1mol), after 6- chloro- 1- hexanols (0.21mol) are mixed homogeneously with 15mL dehydrated alcohol
It is added dropwise in system under vigorous stirring, Deca 5min is warming up to 75 DEG C after finishing, insulation reaction 3h.Reaction is cold after terminating
But to room temperature, after vacuum filtration, crude product is dried to obtain twice with distillation washing, purified twice with benzene afterwards, after vacuum drying
To powder solid, yield 75.58%, seal standby.
The synthesis of second step adhesive
(1) by poly-epsilon-caprolactone glycol (molecular weight is 1000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) the poly-epsilon-caprolactone glycol (100g) being dehydrated is added in reactor, is added after being heated to 45 DEG C under agitation
Enter MDI (64g), be warming up to 88 DEG C and insulation reaction 3h, reaction terminates rear vacuum outgass 0.5h, seal intermediate afterwards standby.
(3) adhesive is prepared：Take the intermediate (10g, 90 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (3.35g, 80 DEG C).
The application of the 3rd step adhesive
(1) PVC pieces (100mm × 25mm × 1mm) surface is processed using chemical method, wipes its surface to remove with acetone
The impurity such as surface grease, remove weak interface layer, are put into standby after 65 DEG C of baking oven 10min are dried.
(2) adhesive (5g) of (3) is picked with Glass rod, PVC pieces surface is equably applied to.After placing 25min, by two
The piece PVC pieces place of smearing overlaps, and is put into be tested after 68 DEG C of baking oven 30h under pressure 4000Pa.Room temperature is peeled off strong after placing one week
Spend for 151.50N 2.5cm-1, compare with comparative example 2 and improve 144.35%.
Example 12
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 15%NaOH aqueous solutions are added
(84g) with biphenyl -4,4 '-mercaptan (0.1mol), after 6- chloro- 1- hexanols (0.22mol) are mixed homogeneously with 25mL dehydrated alcohol
It is added dropwise in system under vigorous stirring, Deca 8min is warming up to 90 DEG C after finishing, insulation reaction 3h.Reaction is cold after terminating
But to room temperature, after vacuum filtration, crude product is dried to obtain twice with distillation washing, purified twice with benzene afterwards, after vacuum drying
To powder solid, yield 82.92%, seal standby.
The synthesis of second step adhesive
(1) by poly adipate succinic acid ester (molecular weight is 2000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) poly adipate succinic acid ester being dehydrated (100g) is added in reactor, after being heated to 45 DEG C under agitation
MDI (64g) is added, 90 DEG C and insulation reaction 2.5h is warming up to, reaction terminates rear vacuum outgass 0.5h, seal intermediate afterwards standby
With.
(3) adhesive is prepared：Take the intermediate (10g, 100 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (2.73g, 95 DEG C).
The application of the 3rd step adhesive
(1) rubber sample (100mm × 25mm × 1mm) surface is processed using chemical method, its table is wiped with tetrahydrofuran
Face removes weak interface layer to remove the impurity such as surface grease, is put into standby after 68 DEG C of baking oven 10min are dried.
(2) adhesive (6g) of (3) is picked with Glass rod, rubber sample surface is equably applied to.After placing 25min,
The two panels sample place of smearing is overlapped, is put under pressure 3800Pa to be tested after 70 DEG C of baking oven 25h.Room temperature is peeled off after placing one week
Intensity is 149.75N 2.5cm-1, compare with comparative example 2 and improve 141.53%
Example 13
The synthesis of first step sulfur-bearing chain extender
In four mouthfuls of reaction bulbs equipped with thermometer, motor stirrer and reflux condensing tube, 10%NaOH aqueous solutions are added
(112g) with Isosorbide-5-Nitrae-benzene dimethanethiol (0.1mol), 6- chloro- 1- hexanols (0.21mol) are mixed homogeneously with 24.5mL dehydrated alcohol
It is added dropwise under vigorous stirring in system afterwards, Deca 10min is warming up to 85 DEG C after finishing, insulation reaction 3h.Reaction terminates
After be cooled to room temperature, after vacuum filtration with distillation washing be dried to obtain crude product twice, afterwards with benzene purify twice, vacuum drying
After obtain powder solid, yield 81.75% is sealed standby.
The synthesis of second step adhesive
(1) by poly adipate succinic acid ester (molecular weight is 1000) the vacuum dehydration 3h at 120 DEG C, seal standby；
(2) poly adipate succinic acid ester being dehydrated (100g) is added in reactor, after being heated to 45 DEG C under agitation
MDI (70.73g) is added, 90 DEG C and insulation reaction 2h is warming up to, reaction terminates rear vacuum outgass 0.5h, seals intermediate afterwards
It is standby.
(3) adhesive is prepared：Take the intermediate (10g, 95 DEG C) described in (2), the sulfur-bearing chain extender of first step synthesis
Then both mixed and quickly stirred, obtain adhesive by (3.77g, 80 DEG C).
The application of the 3rd step adhesive
(1) using chemical method process leather sample (100mm × 25mm × 1mm) surface, with acetone wipe its surface with
The impurity such as surface grease are removed, weak interface layer is removed, is put into standby after 70 DEG C of baking oven 10min are dried.
(2) adhesive (6g) of (3) is picked with Glass rod, leather sample surface is equably applied to.After placing 25min,
The two panels sample place of smearing is overlapped, is put under pressure 4000Pa to be tested after 70 DEG C of baking oven 24h.Room temperature is peeled off after placing one week
Intensity is 158.50N 2.5cm-1, compare with comparative example 2 and improve 155.64%.
Claims (29)
1. a kind of High-performance adhesive, it is characterised in that adhesive includes polyester-diol, diisocyanate and chain extender, polyester two
The mass ratio of alcohol, diisocyanate and chain extender is 1:0.42:0.25-1:0.85:0.85.
2. a kind of High-performance adhesive as claimed in claim 1, it is characterised in that polyester-diol, diisocyanate and chain extender
Mass ratio be 1:0.51:0.66-1:0.54:0.70.
3. a kind of preparation method of High-performance adhesive as claimed in claim 1 or 2, it is characterised in that comprise the steps：
（1）The synthesis of sulfur-bearing chain extender
In the reactor, add concentration to be 10wt%-30wt% NaOH aqueous solutions and mercaptan, chlorhydrin is mixed with dehydrated alcohol
It is added dropwise in reactor under vigorous stirring after uniform, after Deca 5-10min, is warming up to 60-90 DEG C, insulation reaction 1-3h,
Reaction is cooled to room temperature after terminating, and with distillation washing 2-4 time after vacuum filtration, obtains crude product, purified with benzene after being dried afterwards
2-4 time, after vacuum drying, obtain powder solid；
（2）The synthesis of adhesive
By polyester-diol at 100-120 DEG C vacuum dehydration 1-3h；The polyester-diol being dehydrated is added in reactor, in stirring
Under be heated to 40-50 DEG C after add diisocyanate, be warming up to reaction temperature 80-90 DEG C and insulation reaction 2-3h obtain centre
Body, reaction terminate rear vacuum outgass 0.5-1h, are incubated 80-100 DEG C of intermediate and seal standby；Need to be with heating by sulfur-bearing chain extender
Set fusing, is taken intermediate and is mixed in 80-100 DEG C of quick stirring with the sulfur-bearing chain extender of fusing, adhesive is obtained after reaction.
4. a kind of preparation method of High-performance adhesive as claimed in claim 3, it is characterised in that the（1）Walk the sulfur-bearing to expand
In the synthesis of chain agent, mercaptan functionality used is 2, including 1,3- dimercaptopropanes, Isosorbide-5-Nitrae-succinimide mercaptans, 1,5- pentane disulfide thioalcohols,
1,6- ethanthiols, 2- phenyl -1,3- dimercaptopropanes, 1,4- benzene dimethanethiols, 1,4- benzenethiols, biphenyl -4,4 '-mercaptan or 4,
4 '-dimercapto diphenyl sulfide.
5. a kind of preparation method of High-performance adhesive as claimed in claim 4, it is characterised in that mercaptan is 4,4 '-dimercapto
Diphenyl sulfide or 1,4- benzene dimethanethiols.
6. a kind of preparation method of High-performance adhesive as claimed in claim 3, it is characterised in that the（1）Walk the sulfur-bearing to expand
In the synthesis of chain agent chlorhydrin used include the chloro- 1- ethanol of 2-, trimethylene chlorohydrin, the chloro- n-butyl alcohols of 4-, the chloro- 1- amylalcohols of 5- or
The chloro- 1- hexanols of 6-.
7. a kind of preparation method of High-performance adhesive as claimed in claim 6, it is characterised in that chlorhydrin is the chloro- 1- of 3- third
Alcohol or the chloro- 1- hexanols of 6-.
8. a kind of preparation method of High-performance adhesive as claimed in claim 3, it is characterised in that the（1）Walk the sulfur-bearing to expand
In the synthesis of chain agent, aqueous solution NaOH concentration is to select 10wt%-20wt%.
9. a kind of preparation method of High-performance adhesive as claimed in claim 3, it is characterised in that the（1）Walk the sulfur-bearing to expand
In the synthesis of chain agent, NaOH：Mercaptan：The mol ratio of chlorhydrin is 2.0:1:2.0-5.5:1:2.2.
10. a kind of preparation method of High-performance adhesive as claimed in claim 9, it is characterised in that NaOH：Mercaptan：Chlorhydrin
Mol ratio be 4.2:1:2.10-5.5:1:2.2.
A kind of 11. preparation methoies of High-performance adhesive as claimed in claim 3, it is characterised in that the（1）Walk the sulfur-bearing
In the synthesis of chain extender, chlorhydrin is 1 with dehydrated alcohol mol ratio:1-1:2.5.
12. a kind of preparation methoies of High-performance adhesive as claimed in claim 11, it is characterised in that chlorhydrin and anhydrous second
Alcohol mol ratio is 1:2.0-1:2.5.
A kind of 13. preparation methoies of High-performance adhesive as claimed in claim 3, it is characterised in that the（1）Walk the sulfur-bearing
Time for adding 7-10min in the synthesis of chain extender, reaction temperature 85-90 DEG C, response time 2.5-3h.
A kind of 14. preparation methoies of High-performance adhesive as claimed in claim 3, it is characterised in that the（2）Step is described to gather
Esterdiol includes 10PE27, poly adipate succinic acid ester, polyadipate ethylene glycol and 1,2-propylene glycol ester, polyadipate
Ethylene glycol-butanediol ester, polyadipate hexanediol ester, polyadipate ethylene glycol-DOPCP, poly-epsilon-caprolactone glycol or poly-
Carbonate diol, and polyester-diol molecular weight ranges are 700-2000.
15. a kind of preparation methoies of High-performance adhesive as claimed in claim 14, it is characterised in that polyester-diol is to gather oneself
Succinate adipate, poly-epsilon-caprolactone glycol, molecular weight is 1000-2000.
A kind of 16. preparation methoies of High-performance adhesive as claimed in claim 3, it is characterised in that the（2）Described in step two
Isocyanates include toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate, PPDI, 1,5- naphthalenes two
Isocyanates, hexamethylene diisocyanate or isophorone diisocyanate.
A kind of 17. preparation methoies of High-performance adhesive as claimed in claim 16, it is characterised in that the（2）Described in step two
Isocyanates are 4,4 '-methyl diphenylene diisocyanate.
A kind of 18. preparation methoies of High-performance adhesive as claimed in claim 3, it is characterised in that the（2）The described glue of step
During glutinous agent is prepared, polyester-diol is 85-90 DEG C with di-isocyanate reaction thermotonuses temperature, and the response time is 2.5-3h.
A kind of 19. preparation methoies of High-performance adhesive as claimed in claim 3, it is characterised in that the（2）The described glue of step
During glutinous agent is prepared, the mass ratio of polyester-diol, diisocyanate and chain extender is 1:0.42:0.25-1:0.85:0.85.
20. a kind of preparation methoies of High-performance adhesive as claimed in claim 19, it is characterised in that polyester-diol, two isocyanides
Acid esters is 1 with the mass ratio of chain extender:0.51:0.66-1:0.54:0.70.
A kind of 21. preparation methoies of High-performance adhesive as claimed in claim 3, it is characterised in that the（2）The described glue of step
During glutinous agent is prepared, the temperature range that sulfur-bearing chain extender used need to be melted with heating mantle is 80-100 DEG C.
22. a kind of applications of High-performance adhesive as claimed in claim 1 or 2, it is characterised in that comprise the steps：
（1）With solvent wiping substrate surface to remove the impurity such as surface grease, weak interface layer is removed, standby is dried in 60-70 DEG C
With；
（2）Adhesive is picked with Glass rod, substrate surface is equably applied to, after placing 10-25min, two plate substrates is smeared
Place overlaps, and after being put into 60-70 DEG C of baking oven 20-30h, takes out to be measured under pressure 3500-4000Pa.
23. a kind of applications of High-performance adhesive as claimed in claim 22, it is characterised in that the base material includes plastics, rubber
Glue, leather or timber.
24. a kind of applications of High-performance adhesive as claimed in claim 22, it is characterised in that molten used by the base material treatment
Agent includes acetone, butanone, ethyl acetate, dimethylformamide, dimethyl acetylamide or tetrahydrofuran.
25. a kind of applications of High-performance adhesive as claimed in claim 24, it is characterised in that molten used by the base material treatment
Agent is acetone.
A kind of 26. applications of High-performance adhesive as claimed in claim 22, it is characterised in that the drying of the process base material
Temperature is 65-70 DEG C.
A kind of 27. applications of High-performance adhesive as claimed in claim 22, it is characterised in that adhesive used by the base material
Amount be 0.15-0.35g/cm2。
A kind of 28. applications of High-performance adhesive as claimed in claim 27, it is characterised in that adhesive used by the base material
Amount be 0.25-0.3g/cm2。
A kind of 29. applications of High-performance adhesive as claimed in claim 22, it is characterised in that the standing time 20-
25min, pressure 3800-4000Pa, place temperature 65-70 DEG C, standing time 24-30h.
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2016
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| CN1167803A (en) * | 1997-03-19 | 1997-12-17 | 湖北大学 | Process for producing adhesive for polyurethane shoes by solution method |
| CN101333425A (en) * | 2008-07-04 | 2008-12-31 | 上海联景聚氨酯科技发展有限公司 | Polyurethane binder, preparation method and application thereof |
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| ANNA KULTYS等: "Polyurethanes Containing Sulfur. II. New Thermoplastic Nonsegmented Polyurethanes with Diphenylmethane Unit in Their Structure", 《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》 * |
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