CN102020969A - Bi-component fast-curing polyurethane adhesive and application thereof - Google Patents
Bi-component fast-curing polyurethane adhesive and application thereof Download PDFInfo
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- CN102020969A CN102020969A CN200910057916XA CN200910057916A CN102020969A CN 102020969 A CN102020969 A CN 102020969A CN 200910057916X A CN200910057916X A CN 200910057916XA CN 200910057916 A CN200910057916 A CN 200910057916A CN 102020969 A CN102020969 A CN 102020969A
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Abstract
The invention discloses a bi-component fast-curing polyurethane adhesive, which comprises a polyalcohol composition component A and a modified isocyanate component B, wherein the component A is a polyalcohol composition, which comprises polyether glycol, a cross linking agent, a catalyst for the reaction of polyisocyanates polymer and an active hydrogen-containing compound, an antioxidant, color paste and/or a filler; the component B is modified isocyanate; and the component A and the component B are separately stored, and are matched in a weight ratio of 100:60-100:110 when used. The polyurethane adhesive can be used as a filter element adhesive of an oil filter.
Description
Technical field
The two-pack that the present invention relates to a kind of environmental protection soon admittedly type polyurethane adhesive, its preparation method, with and in the application of oil filter.
Technical background
Along with the high speed development of automotive industry, the demand of high-performing car purifier is presented quick growth.Purifier mainly contains air filter, oil filter, fuel filter three major types.The improvement of oil filter is had higher requirement to use therein tackiness agent, the tackiness agent that uses in the oil filter also will have excellent operation processing characteristics, good temperature resistance energy and oil-proofness, lower toxicity and compliance with environmental protection requirements except the good resistance to air loss that will guarantee filter core filter paper and end cap and be bonded and sealed.This just requires, and scientific workers develop more excellent performances, cost is low, workability is strong, the filter core tackiness agent of health environment-friendly.
Between the filter core of purifier and end cap, need to use tackiness agent to carry out bonding and sealing.At present, the used tackiness agent of purifier mainly contains kinds such as hot melt adhesive, rubber adhesive, bi-component polyurethane ester gum, bi-component epoxy, all contain various softening agent in these materials to some extent, such as, dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DOB) etc.These materials are chemically inert materials, have transport property, and healthy and environment are had potential hazard.Use hot melt adhesive such as PVC adhesive paste, this system viscosity is big, and casting molding machine can't be operated, can only be hand-manipulated, and need at high temperature be cured, not only waste energy but also influence production efficiency.As adopt bi-component epoxy, and this class tackiness agent must on-the-spotly be allocated, and uses up in limited time, and solidification process reached more than 24 hours, and labor capacity is big, production efficiency is low, environmental pollution is serious.In addition, commercially available polyurethane adhesive generally contains clorafin, dioctyl phthalate (DOP) (DOP), 3 at present, 3 '-two chloro-4,4 '-diamino-ditan (MOCA), tolylene diisocyanate compositions such as (TDI), and with the polyethers of routine is that the polyurethane adhesive of base-material can only use down continuously at 120 ℃, be difficult to satisfy oil filter through about 135 ℃ of higher use temperatures of working down of being everlasting, temperature tolerance is poor, and bonding strength is compared defectives such as also on the low side with other structure glue.What people's expectation had high use temperature is the polyurethane adhesive combination of base-material with the polyethers.
Summary of the invention
For overcoming the above-mentioned defective of prior art, one of purpose of the present invention is to provide a kind of two-pack of environmental protection to consolidate type polyurethane adhesive soon, and it can satisfy the performance requriements of oil filter in the medium-term and long-term use of the machine oil of temperature more than 135 ℃.
Another object of the present invention is to provide a kind of above-mentioned two-pack to consolidate the preparation method of type polyurethane adhesive soon.
A further object of the present invention is to provide the application of above-mentioned polyurethane adhesive in oil filter is made, and it is as filter core glue.
For achieving the above object, the present invention adopts following technical scheme:
A kind of two-pack is consolidated type polyurethane adhesive soon, and it comprises polyhydric alcohol composition component A and modified isocyanate B component, wherein
Component A is a polyhydric alcohol composition, comprise: one or more hydroxy functionalities of (1) 100 weight part are more than 3.0 and molecular weight is the polyether glycol of 1000-6000, (2) one or more equivalents of 8-20 weight part are the linking agent below 180, (3) the 1.5-3.0 weight part one or more be used for polyisocyanic acid ester polymer and active hydrogen-contg compound catalyst for reaction, (4) one or more oxidation inhibitor of 0-3.0 weight part, the mill base and/or the filler of (5) 0-3 weight part.
B component is to be the isocyanic ester performed polymer that the polyvalent alcohol of 1000-8000 produces through polyreaction by 100 weight part diphenylmethanediisocyanates (MDI) and 10-80 weight part molecular weight; Or the mixture of this isocyanic ester performed polymer and the formation of other polymeric isocyanate.
Component A and B component are deposited separately, during use by component A: B component is that 100: 60～100: 110 weight ratio is used.
Such as, when this polyurethane adhesive is cured the reaction moulding, component A and B component are by 100: 60-100: 110 weight ratio is cast in the internal surface of element of oil filter end cap after mixing tube mixes through the glue-injection machine of band static mixing tube, levelling, formed at normal temp when treating tackify inserts filter paper, after the curing, between end cap and filter paper, form one deck glue-line, played the effect of bonding and sealing.
The above-mentioned fast preparation method of type bi-component polyurethane adhesive admittedly comprises the steps:
(1) preparation of component A:
1. alkali metal hydroxide or the bimetallic cyanide complex with 1-50 part is catalyzer, at least a low-molecular-weight polyvalent alcohol of 100 weight parts and the propylene oxide and/or the oxyethane of 900-10000 weight part are carried out ring-opening polymerization, then the multipolymer that obtains is made with extra care, filtered, obtaining hydroxyl value is that 150-230mgKOH/g, hydroxy functionality are more than 3.0 and molecular weight is the polyether glycol of 1000-6000;
Be at least a kind of in glycerine, TriMethylolPropane(TMP), tetramethylolmethane, quadrol, Xylitol, sorbyl alcohol, N.F,USP MANNITOL or the sucrose as the low-molecular-weight polyvalent alcohol of initiator.
2. form polyhydric alcohol composition: at least a polyether glycol of 100 weight parts, at least a linking agent of 8-20 weight part, at least a catalyzer of 1.5-3.0 weight part, the oxidation inhibitor of 0-3.0 weight part and the toning mill base of 0-3.0 weight part are mixed, thermal dehydration under 80～110 ℃ temperature, get polyether glycol composition, filling and sealing is standby.
(2) preparation of B component
With one or more molecular weight of one or more diphenylmethanediisocyanates (MDI) of 100 weight parts and 10-80 part be the polyvalent alcohol of 1000-8000 60-80 ℃ of reaction 1-10 hour, generate the isocyanic ester performed polymer; Perhaps this isocyanic ester performed polymer and other polymeric isocyanate are formed mixture.
Compared with prior art, adopt not only power operations (flowability of component A and B component is fit to the glue-injection machine operation of band static mixing tube fully) such as curing speed fast (be generally below 2 hours and get final product curing molding), suitable casting molding machine of polyurethane adhesive, production efficiency height, the waste of material of technical scheme preparation of the present invention few, and the cured article oil resistant that obtains, high temperature resistant, can under 135 ℃ temperature, keep being bonded and sealed of filter core filter paper and end cap for a long time; Simultaneously, because the material that composition of the present invention does not use the non-ambient friendly is such as DOP, DOB, so feature of environmental protection height.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only to be used to the present invention is described and be not used in the scope of the present invention that limits.
The composition of component A and preparation
Component A of the present invention is a polyhydric alcohol composition.In order to improve the oil-proofness and the high thermal resistance of goods behind the composition molding, need in advance synthetic a kind of high functionality polyethers.This special polyether glycol is a kind of polymer novel material, and its hydroxyl value is 150-230mgKOH/g, preferred 170-210mgKOH/g; Hydroxy functionality is more than 3.0, preferred more than 3.5; And molecular weight is 1000-6000, preferred 2000-5000, more preferably 2500-4000.
This polyether glycol is synthetic by the following method: alkali metal hydroxide or bimetallic cyanide complex with 1-50 part are catalyzer, at least a low-molecular-weight polyvalent alcohol of 100 weight parts and the propylene oxide and/or the oxyethane of 900-10000 weight part are carried out ring-opening polymerization, obtain multipolymer.
Low-molecular-weight polyvalent alcohol as the reaction initiator is at least a in glycerine, TriMethylolPropane(TMP), tetramethylolmethane, quadrol, Xylitol, sorbyl alcohol, N.F,USP MANNITOL or the sucrose.
Such as, described polyether glycol be selected from down the group at least a: polyether glycol I (hydroxyl value 178mgKOH/g, molecular weight: 2000, our company's self-control), polyether glycol I I (hydroxyl value 182mgKOH/g, molecular weight: 2000, our company self-control), polyoxytrimethylene ether triol (trade(brand)name: GEP-330N, molecular weight: 5000; Trade(brand)name: GEP-360N, molecular weight: 8000; Trade(brand)name: GSE-3028,6000), PTMG (trade(brand)name: PTMG-1000 molecular weight:, 1000), polycaprolactone glycol (trade(brand)name: P-220, molecular weight: 2000), polycarbonate diol (trade(brand)name: ST-602, molecular weight: 2000) molecular weight:.
Linking agent among the said components A be selected from down at least the group in a kind of: ethylene glycol (EG), 1, ammediol (PG), 1,4-butyleneglycol (BDO), 1,6-hexylene glycol (HG), Resorcinol-two (beta-hydroxyethyl) ether (trade(brand)name: HQEE), diglycol phthalate (trade(brand)name:
PS-3152), diethyl toluene diamine (trade(brand)name: Ethacure-100), 3,5-diformazan sulfenyl tolylene diamine (trade(brand)name: Ethacure-300), 1,4-butanediamine (BDA), 1,6-hexanediamine (HAD), 4,4 '-methylene-bis (2, the 6-diethyl cyclohexylamine) (M-DECA), 4,4 '-methylene-bis (2-ethyl-6-methyl cyclohexylamine) (M-MECA), isophorone diamine (IPDA).
The equivalent of described linking agent is below 180, and is preferred below 160, more preferably below 150.If the equivalent of linking agent is higher than 180, then want to reach the product of same rigidity, certainly will to increase the consumption of linking agent.
In the polyether glycol of 100 weight parts, the content of above-mentioned linking agent is the 8-20 weight part, preferred 10-16 weight part, more preferably 12-15 weight part.If the content of linking agent is less than 8 weight parts, then the solidified product is soft partially, influences the quality of solidifying product; If the content of linking agent is higher than 20 weight parts, then can cause product excessively crosslinked, the consumption of B component is increased, and then increase cost, and can cause disadvantageous effects such as the solidified product is too crisp.
Be used for polyisocyanic acid ester polymer and active hydrogen-contg compound catalyst for reaction among the said components A and be one or more of tertiary amine well known in the art, tin salt and tin thiolate.Such as amine catalyst (trade(brand)name:
EF-600), postpone amine catalyst (trade(brand)name:
EF-602), tin catalyst (trade(brand)name:
UL-1,
UL-32).The usage quantity of catalyzer depends on its catalytic efficiency and required speed of response.
In the polyether glycol of 100 weight parts, the content of above-mentioned catalyzer is the 1.5-3.0 weight part, preferred 2-2.5 weight part.If the content of catalyzer is less than 1.5 weight parts, then do not reach the abundant polymeric effect of component A and B component; If the content of catalyzer is higher than 3 weight parts, then component A and B component polymerizing curable excessive velocities make fully levelling of tackiness agent, cause forming operation inconvenience, and production cost is increased.
The preferred oxidation inhibitor that uses among the said components A.The said oxidation inhibitor of the present invention is hindered phenol such as the tetramethylene (3 of comprising well known in the art, 5-two-tertiary butyl-4-hydroxy phenylpropionic acid) methyl esters, commodity are called antioxidant 1010, triglycol two-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], commodity are called oxidation inhibitor 245; Aromatic amine such as N, N '-diphenyl-para-phenylene diamine; Phosphorous acid ester such as tricresyl phosphite (2, the 4-DI-tert-butylphenol compounds) ester.
In the polyether glycol of 100 weight parts, the content of above-mentioned oxidation inhibitor is the 0-3.0 weight part, preferred 0.5-3.0 weight part, more preferably 0.8-2.5 weight part, more preferably 1-2.0 weight part.If the content of oxidation inhibitor is higher than 3 weight parts, then can causes solidified product mechanical properties decrease and raw materials cost is increased.
Can add an amount of polyurethane adhesive component commonly used among the said components A, such as mill base and/or filler, for the toning mill base, can use present technique field pigment color commonly used, grey can select commodity by name
The mill base of 7-PA/1120; Filler such as lime carbonate, kaolin, talcum powder etc.
When preparation component A, polyether glycol, linking agent, catalyzer, oxidation inhibitor and toning mill base, filler are mixed, thermal dehydration under 80～110 ℃ temperature gets polyhydric alcohol composition, and filling and sealing is standby.Wherein, preferably with mixture thermal dehydration under 80～110 ℃ temperature, more preferably 90-100 ℃.If be lower than 80 ℃, moisture is difficult to remove, and influences the storage cycle; If be higher than 110 ℃ of then easy oxidizing reactions, cause adhesive quality to descend.
The composition of B component and preparation
B component in the polyurethane adhesive of the present invention is a modified isocyanate, and it is the mixture of isocyanic ester performed polymer or isocyanic ester performed polymer and other polymeric isocyanate.
Preferably, B component comprises: one or more diphenylmethanediisocyanates (MDI) of 100 weight parts are the isocyanic ester performed polymer of the polyol blends of 1000-8000 through the polyreaction generation with one or more molecular weight of 10-80 weight part; The mixture of perhaps above-mentioned performed polymer and other polymeric isocyanate.
The diphenylmethanediisocyanate (MDI) that is used to form isocyanic ester performed polymer B component be selected from down the group at least a: 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, carbodiimide diphenylmethanediisocyanate and several mixture in the middle of them.Such as, diphenylmethanediisocyanate can be: 4,4 '-diphenylmethanediisocyanate (trade(brand)name:
1810), 2,4 '-diphenylmethanediisocyanate (trade(brand)name:
3056), the carbodiimide diphenylmethanediisocyanate (trade(brand)name:
2020), many phenylmethanes polyisocyanates (trade(brand)name:
5005).
The polyvalent alcohol molecular weight that is used to form isocyanic ester performed polymer B component is 1000-8000, be selected from down the group at least a: polyether glycol, polyester polyol or their several mixtures.Such as, polyether glycol can be: polyoxytrimethylene ether triol (trade(brand)name: GEP-330N, molecular weight: 5000; Trade(brand)name: GEP-360N, 8000), polyoxytrimethylene ether glycol (trade(brand)name: GEP-2028, molecular weight: 4000), PTMG (trade(brand)name: PTMG-1000, molecular weight: 1000) molecular weight:; For another example, polyester polyol can be: adipate polyester polyvalent alcohol (trade(brand)name: L-144, molecular weight 1000; Trade(brand)name: L-244, molecular weight: 2000), benzoic anhydride polyester polyol (trade(brand)name:
PD-56LV, 2000), polycaprolactone glycol (trade(brand)name: P-220, molecular weight: 2000), polycarbonate diol (trade(brand)name: ST-602, molecular weight: 2000) molecular weight:.
In the MDI of 100 weight parts, the polyvalent alcohol that is used for reacting with MDI is the 10-80 weight part, preferred 15-70 weight part, more preferably 20-60 weight part.If the amount of polyvalent alcohol is higher than 80 weight parts, then can cause the viscosity of B component system to increase, thereby influence the casting molding machine operation, even casting molding machine can't be poured into a mould; If the amount of polyvalent alcohol is less than 10 weight parts, then the performed polymer that forms is stored inadequately and is stablized, and side reaction takes place easily.
B component can also be the mixture that above-mentioned isocyanic ester performed polymer and other polymeric isocyanate form.
The isocyano of the isocyanic ester of preferred ingredient B (NCO) content is 20-31wt%, preferred 22-29wt%, more preferably 23-27wt%.
On the other hand, the preparation of B component can be adopted the confessed polymerization process in this area, such as " plastics industry handbook (urethane): chapter 10 polyurethane elastomer " (Li Junxian chief editor, Chemical Industry Press, the 1st edition, 1999, P406) the related preparation technology of Jie Shaoing.
Specifically, its preparation mainly comprises: earlier polyvalent alcohol is carried out processed, avoid causing because of the existence of water the side reaction generation of polyureas, and then cause the performed polymer quality to descend; Elder generation such as being heated to 60 ℃, avoids the MDI preheating to cause performed polymer molecular weight distribution ununiformity and quality instability greatly because of temperature variation before carrying out polyreaction; Polymeric reaction temperature is controlled at 50-100 ℃, preferred 60-80 ℃; Reaction times is 1-10 hour, is preferably 3-4 hour; After reaction finishes, can carry out filling and sealing.
The use of polyurethane adhesive of the present invention
Polyurethane adhesive of the present invention can adopt single stage method to finish by the static mixing glue-applying technique, component A and B component are placed A, the B batch can of glue-injection machine respectively, keep the batch can temperature at 15-60 ℃, batch can pressure is 2-5MPa, in component A: B component is 100: 60-100: after the ratio of 110 (weight ratios) mixes by static mixing tube, be cast in element of oil filter end cap internal surface, levelling, when treating tackify filter paper is inserted, between end cap and filter paper, formed one deck glue-line, gel time is 30-80 second, self-vulcanizing 4-24h.The end cap preferred substrate comprises metallic material of aluminum, stainless steel, and plastic material has ABS rubber, urethane, polyolefine, polycarbonate, polymeric amide and nylon.
Tackiness agent of the present invention is preferably in the self-vulcanizing moulding.
Adopt technical scheme of the present invention, compare with the filter core glue of prior art, polyurethane adhesive combination of the present invention has conspicuous following advantage:
(1) component A does not contain chemically inert materials such as any solvent and softening agent, has avoided this class material moves and volatilization brings water pollution and atmospheric pollution, thereby makes the material of environment friendly.
(2) B component does not contain TDI, replaces the MDI of safer environmental protection, thereby has avoided the injury of the severe toxicity of TDI to human body.
(3) said composition viscosity is low, can under relatively low temperature, process, and can room temperature fast-curing, glue-applying technique is easy, has significantly reduced energy consumption, has improved production efficiency,
(4) have the bonding strength height, and have the performance of high thermal resistance preferably and excellent anti-machine oil.
Following embodiment will be used for illustrating the present invention, but not be to be used for limiting claim scope of the present invention, except as otherwise noted, be noted that the umber of addressing among the following embodiment all refers to weight part.
The polyurethane adhesive that following each embodiment is obtained carries out the testing evaluation of following technical indicator.
Test index comprises: tensile strength; Elongation at break; Thermal ageing (135 ℃, 500h) back draft intensity; Thermal ageing (135 ℃, 500h) back elongation at break; 180 ° of stripping strengths; Shore A hardness; Non-volatile content; The machine oil weathering test (135 ℃, 192h); Shrinking percentage.
Embodiment 1
1. the preparation of component A
(1) polyether glycol I is synthetic
The mixture of 100 parts of sorbyl alcohols and 2.3 parts of potassium hydroxide is joined in the vacuum reaction still that has stirring, open and stir, heat temperature raising is to 80-100 ℃, be evacuated to then-0.09MPa, remove the moisture in the mixture, then logical nitrogen to tensimeter is zero, and then slowly add 1100 parts propylene oxide, keep 90-120 ℃ of temperature of reaction, reacting kettle inner pressure remains on about 0.4MPa, shows then that when reaction pressure is reduced to zero reaction finishes, obtained the multipolymer of sorbyl alcohol and propylene oxide, after steaming remaining propylene oxide, neutralize, filter then with phosphoric acid, refining, press GB 12008.3-89 test, hydroxyl value is 178mgKOH/g, cooling, and the discharging encapsulation is stand-by.
(2) polyether glycol I I's is synthetic
The mixture of 100 parts of sorbyl alcohols and 3.0 parts of potassium hydroxide is joined in the vacuum reaction still that has stirring, open and stir, heat temperature raising is to 80-100 ℃, be evacuated to then-0.09MPa, remove the moisture in the mixture, then logical nitrogen to tensimeter is zero, and then slowly add 800 parts of propylene oxide, keep 90-120 ℃ of temperature of reaction, when reacting kettle inner pressure does not change, then slowly add 200 parts of oxyethane and continue reaction, finally obtain the multipolymer of sorbyl alcohol and propylene oxide/oxyethane, steam remaining propylene oxide, behind the oxyethane, neutralize, filter then with phosphoric acid, refining, press GB 12008.3-89 test, hydroxyl value is 182mgKOH/g, cooling, and the discharging encapsulation is stand-by.
(3) preparation of component A
Polyether glycol: the self-control polyether glycol I is 100 parts;
Linking agent:
PS-3152 is that 5 parts, Ethacure-300 are that 2 parts, HQEE are 6 parts;
Catalyzer:
EF-600 be 1.5 parts,
UL-1 is 0.8 part;
Oxidation inhibitor: 1010 is 1 part;
The toning mill base:
7-PA/1120 is 2 parts.
Above-mentioned material is joined in the reactor, mix and be heated to 90-110 ℃, be evacuated to-0.09MPa, dewater after 2 hours, the discharging package encapsulation gets final product.
2. B component is synthetic
(4) dehydration of polyvalent alcohol: the polyether glycol PTMG-1000 of capacity is dropped into have in the vacuum reaction still of stirring earlier, be heated to 120 ℃ under stirring, be evacuated to then-0.09MPa, dewatered 120 minutes, it is stand-by to be cooled to room temperature then.
(5) preparation of performed polymer and blending: with 100 parts diphenylmethanediisocyanate
1810 put in another reactor; under nitrogen protection; stirring is warming up to 60 ℃; slowly add (4) set by step then and took off 53 parts of the PTMG-1000 polyether glycols of water; feed rate is the best with temperature of reaction kettle at 80～85 ℃, after waiting to add polyvalent alcohol, continues reaction 2 hours; press GB 12009.4-89 test, NCO content is 19.1%.Then with many phenylmethanes polyisocyanates of 600 parts
5005 add in this reactor, stir, and recording NCO content is 28.7%.Pack after being cooled to room temperature, sealing is deposited.
3. the use of polyurethane adhesive combination
(6) by RIM technology, component A and B component are placed A, the B batch can of glue-injection machine respectively, keep the batch can temperature at 30 ℃, in component A: B component is 100: after the ratio of 85-90 (weight ratio) mixes by static mixing tube, be cast in machine oil filter core end cap internal surface, levelling, when treating tackify filter paper is inserted, the insertion time is not diffused as the best to the filter paper top with tackiness agent, has formed one deck glue-line like this between end cap and filter paper, gel time is about 35 seconds, self-vulcanizing 24h.
Performance by the polyurethane adhesive of above-mentioned processing condition preparation sees Table 1.
Embodiment 2
1. the preparation of component A
Polyether glycol: self-control polyether glycol I I is 100 parts;
Linking agent:
PS-3152 is that 5 parts, Ethacure-300 are that 2 parts, HQEE are 6 parts;
Catalyzer::
EF-600 be 0.9 part,
UL-1 is 0.5 part;
Antioxidant 1010 is 1 part;
The toning mill base:
7-PA/1120 is 2 parts.
Step is with embodiment 1 step (3).
2. B component is synthetic
Diphenylmethanediisocyanate:
2020 is 100 parts; Polyether glycol: PTMG-1000 is 40 parts;
5005 is 420 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 28.1%.
3. the use of polyurethane adhesive
Operation steps and processing condition are with embodiment 1 step 3
Performance by the polyurethane adhesive of above-mentioned processing condition preparation sees Table 1.
Embodiment 3
1. the preparation of component A
Polyether glycol: the self-control polyether glycol I is 40 parts, and self-control polyether glycol I I is 60 parts;
Linking agent:
PS-3152 is that 5 parts, Ethacure-300 are that 2 parts, HQEE are 6 parts;
Catalyzer::
EF-600 be 1.2 parts,
UL-1 is 0.7 part;
Antioxidant 1010 is 1 part;
The toning mill base:
7-PA/1120 is 2 parts.
Step is with embodiment 1 step (3).
2. B component is synthetic
With embodiment 2 steps 2.
3. the use of polyurethane adhesive
Operation steps and processing condition are with embodiment 1 step 3
Performance by the polyurethane adhesive of above-mentioned processing condition preparation sees Table 1.
Embodiment 4
1. the preparation of component A
Polyether glycol: the self-control polyether glycol I is 40 parts, and self-control polyether glycol I I is 50 parts, and PTMG-1000 is 10 parts;
Linking agent:
PS-3152 is that 5 parts, Ethacure-300 are that 2 parts, HQEE are 8 parts;
Catalyzer::
EF-600 be 1.2 parts,
UL-1 is 0.6 part;
Antioxidant 1010 is 1 part;
The toning mill base:
7-PA/1120 is 2 parts.
Step is with embodiment 1 step (3).
2. B component is synthetic
Diphenylmethanediisocyanate:
2020 is 100 parts; Polyester polyol: P-220 is 52 parts;
5005 is 610 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 28.6%.
3. the use of polyurethane adhesive
Operation steps and processing condition are with embodiment 1 step 3
Performance by the polyurethane adhesive of above-mentioned processing condition preparation sees Table 1.
Embodiment 5
1. the preparation of component A
Composition is with embodiment 4
Step is with embodiment 1 step (3)
2. B component is synthetic
Diphenylmethanediisocyanate:
2020 is 60 parts,
1810 is 40 parts;
Polyester polyol: ST-602 is 45 parts;
5005 is 580 parts;
Step is with embodiment 1 step (4) and (5).Press GB 12009.4-89 test, NCO content is: 29.02%.
3. the use of polyurethane composition
Operation steps and processing condition are with embodiment 1 step 3
Performance by the polyurethane adhesive of above-mentioned processing condition preparation sees Table 1.
Embodiment 6
1. the preparation of component A
Polyether glycol: the self-control polyether glycol I is 40 parts, and self-control polyether glycol I I is 50 parts, and PTMG-1000 is 5 parts, and P-220 is 5 parts;
Linking agent:
PS-3152 is that 5 parts, Ethacure-300 are that 3.5 parts, HQEE are 6 parts;
Catalyzer::
EF-600 be 1.0 parts,
UL-1 is 0.7 part;
Antioxidant 1010 is 1 part;
The toning mill base:
7-PA/1120 is 2 parts.
Step is with embodiment 1 step (3).
2. B component is synthetic
Composition is with embodiment 5
Step is with embodiment 5 steps 2
3. the use of polyurethane adhesive
Operation steps and processing condition are with embodiment 1 step 3
Performance by the polyurethane adhesive of above-mentioned processing condition preparation sees Table 1.
The performance index of table 1. polyurethane adhesive
As can be seen from Table 1, the tensile strength of various embodiments of the present invention all 〉=more than the 13MPa; Elongation at break 〉=130%; Thermal ageing back draft intensity (135 ℃, 500h) 〉=12.7MPa; Elongation at break after the thermal ageing (135 ℃, 500h) 〉=120%; Machine oil back draft intensity (135 ℃, soak the 192h) 〉=12.0MPa that wears out, the aging back of machine oil elongation at break (135 ℃ are soaked 192h) 〉=117%; 180 ° of stripping strength 〉=6.9kN/m; Shore A hardness 〉=88; Product does not shrink substantially, volatile matter≤0.8%.As can be seen, polyurethane adhesive of the present invention satisfies the industry standard of oil strainer fully, has broad application prospects.
Though above invention only is applied to the bonding of machine oil filter core filter paper and end cap.But the present invention undoubtedly can extend to other near field, and as bonding of furniture industry, shoemaking industry, architectural leak stopping joint filling, Furniture panel etc., this is conspicuous for a person skilled in the art.Therefore, under thought of the present invention, those skilled in the art can make various changes or modification to the present invention on this basis, should belong to scope of the present invention equally.
Claims (10)
1. a two-pack is consolidated type polyurethane adhesive soon, and it comprises polyhydric alcohol composition component A and modified isocyanate B component, wherein
Component A is a polyhydric alcohol composition, comprises: one or more hydroxy functionalities of 100 weight parts are more than 3.0 and molecular weight is the polyether glycol of 1000-6000; One or more equivalents of 8-20 weight part are the linking agent below 180; 1.5-3.0 one or more are used for polyisocyanic acid ester polymer and active hydrogen-contg compound catalyst for reaction weight part; 0-3.0 one or more oxidation inhibitor of weight part; The mill base of 0-3 weight part and/or filler.
B component is to be the isocyanic ester performed polymer that the polyvalent alcohol of 1000-8000 produces through polyreaction by one or more diphenylmethanediisocyanates of 100 weight parts and one or more molecular weight of 10-80 weight part; The perhaps mixture of this isocyanic ester performed polymer and other polymeric isocyanate.
Component A and B component are deposited separately, during use by component A: B component is that 100: 60～100: 110 weight ratio is used.
2. polyurethane adhesive according to claim 1, it is characterized in that, described polyether glycol is that the propylene oxide of at least a low molecular weight polyols of 100 weight parts and 900-10000 weight part and/or oxyethane carry out ring-opening polymerization and the multipolymer that obtains, and described low molecular weight polyols is selected from down group: TriMethylolPropane(TMP), tetramethylolmethane, quadrol, Xylitol, sorbyl alcohol, N.F,USP MANNITOL and sucrose.
3. polyurethane adhesive according to claim 1 is characterized in that, described polyether glycol hydroxyl value is 150-230mgKOH/g.
4. polyurethane adhesive according to claim 1 is characterized in that, described polyether glycol is that hydroxyl value is that 178mgKOH/g, molecular weight are that the I or the hydroxyl value of 2000 polyether glycols is that 182mgKOH/g, molecular weight are 2000 polyether glycol I I.
5. polyurethane adhesive according to claim 1 is characterized in that, the isocyano-content of described B component is 20-31wt%.
6. polyurethane adhesive according to claim 1, it is characterized in that, described diphenylmethanediisocyanate be selected from down the group at least a: 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, carbodiimide diphenylmethanediisocyanate.
7. polyurethane adhesive according to claim 1 is characterized in that, described polyvalent alcohol be selected from down the group at least a: polyether glycol, polyester polyol or their mixture.
8. a method for preparing as each described polyurethane adhesive in the claim 1 to 6 comprises the steps:
(1) preparation of component A:
1. synthesizing polyether glycol
Alkali metal hydroxide or bimetallic cyanide complex with 1-50 are catalyzer, at least a low-molecular-weight polyvalent alcohol of 100 weight parts and the propylene oxide and/or the oxyethane of 900-10000 weight part are carried out ring-opening polymerization, then the multipolymer that obtains is made with extra care, filtered, obtain the polyether glycol that hydroxyl value is 150-230mgKOH/g;
2. form polyhydric alcohol composition
Described polyvalent alcohol, linking agent, catalyzer, oxidation inhibitor and mill base and/or filler are mixed, and thermal dehydration under 80～110 ℃ temperature gets polyhydric alcohol composition, and filling and sealing is standby;
(2) preparation B component
Described diphenylmethanediisocyanate and described polyvalent alcohol were reacted 1-10 hour at 60-80 ℃, generate the isocyanic ester performed polymer; Perhaps this isocyanic ester performed polymer and other polymeric isocyanate are formed mixture;
Component A and B component are deposited separately.
9. according to the application of each described bi-component polyurethane adhesive in the claim 1 to 6 in oil filter is made.
10. application according to claim 9, it is characterized in that, described component A and B component are placed A, the B batch can of glue-injection machine respectively, keep the batch can temperature at 15-60 ℃, batch can pressure is 2-5MPa, by the static mixing glue-applying technique, by component A: B component is 100: 60-100: after 110 weight ratio mixes by static mixing tube, be cast in the clear device filter core of machine oil end cap internal surface, levelling when treating tackify inserts filter paper, has formed one deck glue-line between end cap and filter paper, gel time is 30-80 second, self-vulcanizing 4-24 hour.
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| CN200910057916XA CN102020969A (en) | 2009-09-18 | 2009-09-18 | Bi-component fast-curing polyurethane adhesive and application thereof |
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| CN200910057916XA CN102020969A (en) | 2009-09-18 | 2009-09-18 | Bi-component fast-curing polyurethane adhesive and application thereof |
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Application publication date: 20110420 |