CN107254028A - Novel alkyl phenol resin viscosified for polyurethane adhesive and preparation method thereof - Google Patents
Novel alkyl phenol resin viscosified for polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN107254028A CN107254028A CN201710431298.5A CN201710431298A CN107254028A CN 107254028 A CN107254028 A CN 107254028A CN 201710431298 A CN201710431298 A CN 201710431298A CN 107254028 A CN107254028 A CN 107254028A
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/36—Chemically modified polycondensates by etherifying
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention belongs to tackifier technical field, more particularly it relates to a kind of Novel alkyl phenol resin viscosified for polyurethane adhesive and preparation method thereof.Described is used for the preparation method for the Novel alkyl phenol resin that polyurethane adhesive is viscosified, and at least comprises the following steps：In the basic conditions, polycondensation reaction is carried out using p-t-butyl phenol, formaldehyde as raw material, obtains A resins；A resins are dissolved in ketones solvent again, alkylating reagent, catalyst is added, wherein, alkylating reagent and A resins carry out phenolic hydroxyl group etherification reaction, obtain the Novel alkyl phenol resin viscosified for polyurethane adhesive.
Description
Technical field
The invention belongs to tackifier technical field, more particularly it relates to a kind of for the new of polyurethane adhesive thickening
Type alkyl phenol resin and preparation method thereof.
Background technology
For a long time, in order to improve the viscosity of adhesive, in different times, people have developed different by every means
Tackifier kind, wherein having rosin and its ester, terpene resin, coumarone indene resin, Petropols and alkyl phenolic resin etc..According to
Document announcement, resin of the Alkylphenolic Tackifying Resin especially based on the phenol containing tertiary carbon atom in the contraposition of phenolic hydroxyl group
Efficient Adhesive Promotion is best.But in the prior art, the technological process of the Alkylphenolic Tackifying Resin of synthesis is more complicated, and by-product
Thing is more.With the development of adhesive, the usage amount of tackifier also increases sharply, and its application field expands day by day in addition, processing
Technology is improved constantly, and the requirement more and more higher to adhesive performance makes people recognize the importance of tackifier further, urgent to expect
The appearance of new, efficient tackifier.
The content of the invention
In order to solve the above-mentioned technical problem, one side of the invention provides a kind of for the new of polyurethane adhesive thickening
Alkyl phenol resin, described Novel alkyl phenol resin has following structural formula：
The R is the alkyl that carbon number is 1~10；
The n is 2~10.
As a kind of preferred technical scheme of the present invention, the R is the alkyl that carbon number is 1~2.
It is described to be used for the soft of the Novel alkyl phenol resin that polyurethane adhesive is viscosified as a kind of preferred technical scheme of the present invention
It is 90~130 DEG C to change point.
The second aspect of the invention, which is provided, is used for the preparation method for the Novel alkyl phenol resin that polyurethane adhesive is viscosified, extremely
Comprise the following steps less：
In the basic conditions, polycondensation reaction is carried out using p-t-butyl phenol, formaldehyde as raw material, obtains A resins；
A resins are dissolved in ketones solvent again, alkylating reagent, catalyst is added, wherein, alkylating reagent and A resins
Phenolic hydroxyl group etherification reaction is carried out, the Novel alkyl phenol resin viscosified for polyurethane adhesive is obtained.
In this product, what is obtained is used for the Novel alkyl phenol resin that polyurethane adhesive is viscosified, and is named as trade mark HA-2017.
As a kind of preferred technical scheme of the present invention, the alkylating reagent is selected from：Iodomethane, chloromethanes, bromomethane,
Dimethyl suflfate, iodoethane, chloroethanes, bromoethane, dithyl sulfate, iodopropane, chloropropane, N-Propyl Bromide, dipropyl sulfate, iodine
Butane, chlorobutane, NBB, dibutyl sulfate, iodopentane, chloropentane, bromo pentane silane, diamyl sulfates, iodohexane, chlorohexane,
Any one or a few mixing in bromohexane, sulfuric acid dihexyl.
As a kind of preferred technical scheme of the present invention, the ketones solvent is selected from：Any one in MEK, acetone
Or several mixing.
As a kind of preferred technical scheme of the present invention, the catalyst is N- (2- aminoethyls) -3- aminopropyl trimethoxies
Base silane, 3- aminopropyl triethoxysilanes are while modified SBA-15.
It is used as a kind of preferred technical scheme of the present invention, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3-
Aminopropyl triethoxysilane is simultaneously in modified SBA-15, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyls
Weight ratio between triethoxysilane and SBA-15 is：3：1：10.
The third aspect of the invention provide it is a kind of for polyurethane adhesive viscosify Novel alkyl phenol resin adhesive,
Coating, ink, the application of rubber materials.
The fourth aspect of the invention provides a kind of adhesive compound, in parts by weight, at least including following components,
With reference to above and other feature, aspect and the advantage described further below that the present invention is more readily understood.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item or event that describe thereafter may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific
Quantity, includes the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.In some examples, approximately
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
In order to solve the above-mentioned technical problem, one side of the invention provides a kind of for the new of polyurethane adhesive thickening
Alkyl phenol resin, described Novel alkyl phenol resin has following structural formula：
The R is the alkyl that carbon number is 1~10；
The n is 2~10.
As a kind of preferred technical scheme of the present invention, the R is the alkyl that carbon number is 1~2.
It is described to be used for the soft of the Novel alkyl phenol resin that polyurethane adhesive is viscosified as a kind of preferred technical scheme of the present invention
It is 90~130 DEG C to change point.
The second aspect of the invention, which is provided, is used for the preparation method for the Novel alkyl phenol resin that polyurethane adhesive is viscosified, extremely
Comprise the following steps less：
In the basic conditions, polycondensation reaction is carried out using p-t-butyl phenol, formaldehyde as raw material, obtains A resins；
A resins are dissolved in ketones solvent again, alkylating reagent, catalyst is added, wherein, alkylating reagent and A resins
Phenolic hydroxyl group etherification reaction is carried out, the Novel alkyl phenol resin viscosified for polyurethane adhesive is obtained.
As a kind of preferred technical scheme of the present invention, the alkylating reagent is selected from：Iodomethane, chloromethanes, bromomethane,
Dimethyl suflfate, iodoethane, chloroethanes, bromoethane, dithyl sulfate, iodopropane, chloropropane, N-Propyl Bromide, dipropyl sulfate, iodine
Butane, chlorobutane, NBB, dibutyl sulfate, iodopentane, chloropentane, bromo pentane silane, diamyl sulfates, iodohexane, chlorohexane,
Any one or a few mixing in bromohexane, sulfuric acid dihexyl.
As a kind of preferred technical scheme of the present invention, the ketones solvent is selected from：Any one in MEK, acetone
Or several mixing.
As a kind of preferred technical scheme of the present invention, the catalyst is N- (2- aminoethyls) -3- aminopropyl trimethoxies
Base silane, 3- aminopropyl triethoxysilanes are while modified SBA-15.
It is used as a kind of preferred technical scheme of the present invention, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3-
Aminopropyl triethoxysilane is simultaneously in modified SBA-15, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyls
Weight ratio between triethoxysilane and SBA-15 is：3：1：10.
" N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously modified for term
SBA-15 " refers to N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes while being grafted to
SBA-15 surface.
Because there be substantial amounts of silicone hydroxyl on SBA-15 surface, wherein, N- (2- aminoethyls) -3- aminopropyl trimethoxy silicon
Alkane, 3- aminopropyl triethoxysilanes can be grafted after hydrolysis with the silicone hydroxyl on SBA-15 surfaces.The SBA-15
Obtained to be commercially available, be purchased from Nanjing Xian Feng Nono-material Science ＆ Technology Ltd..
In a preferred embodiment, N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyls
Triethoxysilane is while the preparation method of modified SBA-15 is as follows：
(1) 10g SBA-15 are added in 300ml toluene solutions, ultrasonic disperse is uniform, standby；
(2) 3g N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 1g 3- aminopropyl triethoxysilanes are added
Into 100ml toluene solutions, and it is 20% triethylamine solution to add 30ml to add volumetric concentration, at 40 DEG C, stirs 2h, standby
With；
(3) solution obtained in step (2) is added to the solution obtained in step (1), the back flow reaction at 100 DEG C
2h, filtering, ethanol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, the ethoxy of 3- aminopropyls three
Base silane is while modified SBA-15.
The third aspect of the invention provide it is a kind of for polyurethane adhesive viscosify Novel alkyl phenol resin adhesive,
Coating, ink, the application of rubber materials.
In the application, the described application field for being used for the Novel alkyl phenol resin that polyurethane adhesive is viscosified is not limited to gluing
Agent, coating, ink, rubber materials.
The fourth aspect of the invention provides a kind of adhesive compound, in parts by weight, at least including following components,
The Novel alkyl phenol resin viscosified for polyurethane adhesive has following structural formula：
The R is the alkyl that carbon number is 1~10；
The n is 2~10.
The R is the alkyl that carbon number is 1~2.
The softening point of the Novel alkyl phenol resin viscosified for polyurethane adhesive is 90~120 DEG C.
The preparation method of the Novel alkyl phenol resin viscosified for polyurethane adhesive, at least comprises the following steps：
In the basic conditions, polycondensation reaction is carried out using p-t-butyl phenol, formaldehyde as raw material, obtains A resins；
A resins are dissolved in ketones solvent again, alkylating reagent, catalyst is added, wherein, alkylating reagent and A resins
Phenolic hydroxyl group etherification reaction is carried out, the Novel alkyl phenol resin viscosified for polyurethane adhesive is obtained.
The alkylating reagent is selected from：Iodomethane, chloromethanes, bromomethane, dimethyl suflfate, iodoethane, chloroethanes, bromine second
Alkane, dithyl sulfate, iodopropane, chloropropane, N-Propyl Bromide, dipropyl sulfate, iodobutane, chlorobutane, NBB, the fourth of sulfuric acid two
It is any one in ester, iodopentane, chloropentane, bromo pentane silane, diamyl sulfates, iodohexane, chlorohexane, bromohexane, sulfuric acid dihexyl
Plant or several mixing.
The ketones solvent is selected from：Any one or a few mixing in MEK, acetone.
The catalyst is N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are same
When modified SBA-15.
N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously modified
In SBA-15, between N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes and SBA-15
Weight ratio is：3：1：10.
N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously modified
SBA-15 preparation method is as follows：
(1) 10g SBA-15 are added in 300ml toluene solutions, ultrasonic disperse is uniform, standby；
(2) 3g N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 1g 3- aminopropyl triethoxysilanes are added
Into 100ml toluene solutions, and it is 20% triethylamine solution to add 30ml to add volumetric concentration, at 40 DEG C, stirs 2h, standby
With；
(3) solution obtained in step (2) is added to the solution obtained in step (1), the back flow reaction at 100 DEG C
2h, filtering, ethanol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, the ethoxy of 3- aminopropyls three
Base silane is while modified SBA-15.
The nitrogen hyper branched polyphosphate ester is purchased from Wuhan hyperbranched resin Co., Ltd, and product grade is HPP-101.
What described solvent can be enumerated has：Dichloroethanes, ethyl acetate, butanone etc..
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available.
Embodiment 1
Embodiment 1 provides a kind of Novel alkyl phenol resin viscosified for polyurethane adhesive, described Novel alkyl phenol tree
Fat has following structural formula：
The R is that carbon number is methyl；
The preparation method of Novel alkyl phenol resin that is viscosified for polyurethane adhesive is：
In tri- mouthfuls of reaction bulbs of 2L, it is 37% formaldehyde to add 450g p-t-butyl phenols, 25.4g sodium carbonate, 608g concentration,
Begin to warm up, when temperature of charge rises to 75 DEG C, open stirring, 96 ± 2 DEG C are reacted 3 hours, reaction completes to add 600ml toluene,
Stirring 10 minutes, stands branch vibration layer, and 200ml water is added in toluene layer.Under stirring, 31% hydrochloric acid of dropwise addition to PH ﹦ 5, then it is quiet
Put branch vibration layer, then with 100ml water washings toluene layer once, point remove wash water, toluene layer is moved into cucurbit, first normal pressure, after subtract
Pressure is distilled to recover toluene, when distilling to vial material temperature degree to 150 DEG C, stops steaming, material is poured into stainless steel disc, naturally cold
But, the faint yellow thermosetting alkyl phenol resins of 562g (hereinafter referred to as A resins) are obtained；
In tetra- mouthfuls of reaction bulbs of 500ml, add after 50g A resins, 150ml acetone, heating, stirring and dissolving, add 3g and urge
Under agent, reflux state, 50g iodomethane is dripped off within 15 minutes, is flowed back 3.5 hours, stops reaction after A resin fundamental reactions are complete, is changed to
Acetone (can apply mechanically next time) is distilled to recover, is evaporated after acetone, 100ml water is added, 100ml toluene is stirred 20 minutes, is stood, point
Water-yielding stratum, toluene layer is washed with water 1 time, divides and removes wash water, and organic phase elder generation normal pressure, rear vacuum distillation is reclaimed toluene, steamed to 145 DEG C -150
DEG C when, stop steam, blowing is in stainless steel disc, natural cooling, obtains 53.5g penaks, 95 DEG C of softening point.
N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously modified
SBA-15 preparation method is as follows：
(1) 10g SBA-15 are added in 300ml toluene solutions, ultrasonic disperse is uniform, standby；
(2) 3g N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 1g 3- aminopropyl triethoxysilanes are added
Into 100ml toluene solutions, and it is 20% triethylamine solution to add 30ml to add volumetric concentration, at 40 DEG C, stirs 2h, standby
With；
(3) solution obtained in step (2) is added to the solution obtained in step (1), the back flow reaction at 100 DEG C
2h, filtering, ethanol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, the ethoxy of 3- aminopropyls three
Base silane is while modified SBA-15.
Embodiment 2
Embodiment 2 provides a kind of Novel alkyl phenol resin viscosified for polyurethane adhesive, described Novel alkyl phenol tree
Fat has following structural formula：
The R is that carbon number is methyl；
The preparation method of Novel alkyl phenol resin that is viscosified for polyurethane adhesive is：
In tri- mouthfuls of reaction bulbs of 2L, it is 37% formaldehyde to add 450g p-t-butyl phenols, 25.4g sodium carbonate, 608g concentration,
Begin to warm up, when temperature of charge rises to 75 DEG C, open stirring, 96 ± 2 DEG C are reacted 3 hours, reaction completes to add 600ml toluene,
Stirring 10 minutes, stands branch vibration layer, and 200ml water is added in toluene layer.Under stirring, 31% hydrochloric acid of dropwise addition to PH ﹦ 5, then it is quiet
Put branch vibration layer, then with 100ml water washings toluene layer once, point remove wash water, toluene layer is moved into cucurbit, first normal pressure, after subtract
Pressure is distilled to recover toluene, when distilling to vial material temperature degree to 150 DEG C, stops steaming, material is poured into stainless steel disc, naturally cold
But, the faint yellow thermosetting alkyl phenol resins of 562g (hereinafter referred to as A resins) are obtained；
In tetra- mouthfuls of reaction bulbs of 500ml, add after 50g A resins, 150ml acetone, heating, stirring and dissolving, add 3g and urge
Under agent, reflux state, 46.4g dimethyl suflfates are dripped off within 15 minutes, are flowed back 3.5 hours, stop anti-after A resin fundamental reactions are complete
Should, it is changed to be distilled to recover acetone (can apply mechanically next time), is evaporated after acetone, add 100ml water, 100ml toluene is stirred 20 minutes,
Stand, separate water layer, toluene layer is washed with water 1 time, divide and remove wash water, organic phase elder generation normal pressure, rear vacuum distillation is reclaimed toluene, steamed extremely
At 145 DEG C -150 DEG C, stop steaming, blowing is in stainless steel disc, natural cooling, obtains 57.8g penaks, 101 DEG C of softening point.
N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously modified
SBA-15 preparation method is as follows：
(1) 10g SBA-15 are added in 300ml toluene solutions, ultrasonic disperse is uniform, standby；
(2) 3g N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 1g 3- aminopropyl triethoxysilanes are added
Into 100ml toluene solutions, and it is 20% triethylamine solution to add 30ml to add volumetric concentration, at 40 DEG C, stirs 2h, standby
With；
(3) solution obtained in step (2) is added to the solution obtained in step (1), the back flow reaction at 100 DEG C
2h, filtering, ethanol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, the ethoxy of 3- aminopropyls three
Base silane is while modified SBA-15.
Comparative example 1
Comparative example 1 is same as Example 1, and difference is, is added without catalyst.
Comparative example 2
Comparative example 2 is same as Example 1, and difference is, is N- (2- aminoethyls) -3- aminopropyls three by catalyst change
Methoxy silane.
Comparative example 3
Comparative example 3 is same as Example 1, and difference is, is 3- aminopropyl triethoxysilanes by catalyst change.
Comparative example 4
Comparative example 4 is same as Example 1, and difference is, is SBA-15 by catalyst change.
Comparative example 5
Comparative example 5 is same as Example 1, and difference is, is triethylamine by catalyst change.
Performance test：
1st, in the synthetic method of testing example 1~2 and comparative example 1~5, the etherificate of phenolic hydroxyl group in p-t-butyl phenol
The conversion ratio of rate, as p-t-butyl phenol.
The test result of table 1
| Embodiment | The etherificate rate of phenolic hydroxyl group in p-t-butyl phenol |
| Embodiment 1 | 100% |
| Embodiment 2 | 100% |
| Comparative example 1 | 30% |
| Comparative example 2 | 52% |
| Comparative example 3 | 46% |
| Comparative example 4 | 38% |
| Comparative example 5 | 55% |
Embodiment 3
Embodiment 3 provides a kind of adhesive compound, in parts by weight, at least including following components,
The preparation method of Novel alkyl phenol resin that is viscosified for polyurethane adhesive is：
In tri- mouthfuls of reaction bulbs of 2L, it is 37% formaldehyde to add 450g p-t-butyl phenols, 25.4g sodium carbonate, 608g concentration,
Begin to warm up, when temperature of charge rises to 75 DEG C, open stirring, 96 ± 2 DEG C are reacted 3 hours, reaction completes to add 600ml toluene,
Stirring 10 minutes, stands branch vibration layer, and 200ml water is added in toluene layer.Under stirring, 31% hydrochloric acid of dropwise addition to PH ﹦ 5, then it is quiet
Put branch vibration layer, then with 100ml water washings toluene layer once, point remove wash water, toluene layer is moved into cucurbit, first normal pressure, after subtract
Pressure is distilled to recover toluene, when distilling to vial material temperature degree to 150 DEG C, stops steaming, material is poured into stainless steel disc, naturally cold
But, the faint yellow thermosetting alkyl phenol resins of 562g (hereinafter referred to as A resins) are obtained；
In tetra- mouthfuls of reaction bulbs of 500ml, add after 50g A resins, 150ml acetone, heating, stirring and dissolving, add 3g and urge
Under agent, reflux state, 46.4g dimethyl suflfates are dripped off within 15 minutes, are flowed back 3.5 hours, stop anti-after A resin fundamental reactions are complete
Should, it is changed to be distilled to recover acetone (can apply mechanically next time), is evaporated after acetone, add 100ml water, 100ml toluene is stirred 20 minutes,
Stand, separate water layer, toluene layer is washed with water 1 time, divide and remove wash water, organic phase elder generation normal pressure, rear vacuum distillation is reclaimed toluene, steamed extremely
At 145 DEG C -150 DEG C, stop steaming, blowing is in stainless steel disc, natural cooling, obtains 57.8g penaks, 101 DEG C of softening point.
N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously modified
SBA-15 preparation method is as follows：
(1) 10g SBA-15 are added in 300ml toluene solutions, ultrasonic disperse is uniform, standby；
(2) 3g N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 1g 3- aminopropyl triethoxysilanes are added
Into 100ml toluene solutions, and it is 20% triethylamine solution to add 30ml to add volumetric concentration, at 40 DEG C, stirs 2h, standby
With；
(3) solution obtained in step (2) is added to the solution obtained in step (1), the back flow reaction at 100 DEG C
2h, filtering, ethanol is washed 3 times, is dried to obtain N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, the ethoxy of 3- aminopropyls three
Base silane is while modified SBA-15.
The preparation method of the adhesive compound is as follows：
Novel alkyl phenol resin, nitrogen hyper branched polyphosphate ester, the solvent viscosified by polyurethane resin, for polyurethane adhesive
Butanone is collectively disposed in stirred tank, and rise temperature is to 50 DEG C, and stirring reaction 2h obtains adhesive compound.
Comparative example 6
Comparative example 6 is same as Example 3, and difference is, not the Novel alkyl phenol tree including being viscosified for polyurethane adhesive
Fat.
Comparative example 7
Comparative example 7 is same as Example 3, and difference is, not including nitrogen hyper branched polyphosphate ester.
Comparative example 8
Comparative example 8 is same as Example 3, and difference is, by the Novel alkyl phenol resin viscosified for polyurethane adhesive more
Change terpene resin into.
Comparative example 9
Comparative example 9 is same as Example 3, and difference is, by the Novel alkyl phenol resin viscosified for polyurethane adhesive more
Change Petropols into.
Comparative example 10
Comparative example 10 is same as Example 3, and difference is, by the Novel alkyl phenol resin viscosified for polyurethane adhesive more
Change octyl group phenolic tackifying resins into.
Comparative example 11
Comparative example 11 is same as Example 3, and difference is, by the Novel alkyl phenol resin viscosified for polyurethane adhesive more
Change tert butyl phenolic resin into.
Performance test
1st, peeling force：By the product in embodiment 3 and comparative example 6~11 and isocyanate curing agent according to 100：5
Ratio is mixed, then mixture is sprayed in PVC base and on aluminium sheet respectively, and quantity for spray is 100g/m2, then at 100 DEG C
10s is toasted in baking oven, PVC base and aluminium sheet are bonded together, after room temperature is placed 24 hours, glued membrane is carried out and carries out peeling force
Performance test.
2nd, Hygrothermal Properties：Under 100% relative humidity, 120 DEG C are risen to from 30 DEG C, 10h is kept；Drop to from 120 DEG C-
40 DEG C, under 30% relative humidity, keep 12h；50 DEG C are risen to from -40 DEG C, under relative humidity 30%, 1h, this mistake is kept
Journey is a circulation, and the test of peeling force is carried out to glued membrane；So carry out after 10 circulations, to glued membrane 90 degree of peeling forces of progress
Test.
3rd, by by the product in embodiment 3 and comparative example 6~11 in outdoor placement 60 days, testing time section：Chongqing, 7
Whether the moon~August part, observation product there is discoloration.
The test result of table 2
The etherificate rate of phenolic hydroxyl group reaches 100% in this synthetic method, raw material p-t-butyl phenol, and the solvent used can be returned
Receipts are applied mechanically, and giving up, Organic substance in water is few, and concentration is low, and no waste gas and waste residue are produced.I.e. three-waste pollution is small is easy to environmental protection treatment, operation letter
Just, it is adapted to industrialized production.
HA-2017 is used in polyurethane adhesive, has preferable 90 degree of peeling forces, and warp for bonding PVC and aluminium sheet
Cross after weatherability test, still with preferable 90 degree of peeling forces, and polyurethane adhesive does not redden constant Huang, without any color
Difference.Thus there is provided the beneficial effect of the application.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim is covered.
Claims (10)
1. a kind of Novel alkyl phenol resin viscosified for polyurethane adhesive, it is characterised in that described Novel alkyl phenol resin tool
There is following structural formula：
The R is the alkyl that carbon number is 1~10；
The n is 2~10.
2. the Novel alkyl phenol resin viscosified as claimed in claim 1 for polyurethane adhesive, it is characterised in that the R is carbon
Atomicity is 1~2 alkyl.
3. the Novel alkyl phenol resin viscosified as claimed in claim 1 for polyurethane adhesive, it is characterised in that described to be used to gather
The softening point of the Novel alkyl phenol resin of urethane glue thickening is 90~130 DEG C.
4. being used for the preparation method for the Novel alkyl phenol resin that polyurethane adhesive is viscosified as described in claims 1 to 3, its feature exists
In at least comprising the following steps：
In the basic conditions, polycondensation reaction is carried out using p-t-butyl phenol, formaldehyde as raw material, obtains A resins；
A resins are dissolved in ketones solvent again, alkylating reagent, catalyst is added, wherein, alkylating reagent and A resins are carried out
Phenolic hydroxyl group etherification reaction, obtains the Novel alkyl phenol resin viscosified for polyurethane adhesive.
5. the preparation method of the Novel alkyl phenol resin viscosified as claimed in claim 4 for polyurethane adhesive, it is characterised in that
The alkylating reagent is selected from：Iodomethane, chloromethanes, bromomethane, dimethyl suflfate, iodoethane, chloroethanes, bromoethane, sulfuric acid
Diethylester, iodopropane, chloropropane, N-Propyl Bromide, dipropyl sulfate, iodobutane, chlorobutane, NBB, dibutyl sulfate, iodine penta
Any one or a few in alkane, chloropentane, bromo pentane silane, diamyl sulfates, iodohexane, chlorohexane, bromohexane, sulfuric acid dihexyl
Mixing.
6. the preparation method of the Novel alkyl phenol resin viscosified as claimed in claim 4 for polyurethane adhesive, it is characterised in that
The ketones solvent is selected from：Any one or a few mixing in MEK, acetone.
7. the preparation method of the Novel alkyl phenol resin viscosified as claimed in claim 4 for polyurethane adhesive, it is characterised in that
The catalyst is that N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously modified
SBA-15。
8. the preparation method of the Novel alkyl phenol resin viscosified as claimed in claim 7 for polyurethane adhesive, it is characterised in that
N- (2- the aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes are simultaneously in modified SBA-15, N-
Weight ratio between (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes and SBA-15 is：3：
1：10.
9. as described in claims 1 to 3 be used for polyurethane adhesive viscosify Novel alkyl phenol resin adhesive, coating, ink,
The application of rubber materials.
10. a kind of adhesive compound, in parts by weight, it is characterised in that at least including following components,
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721697A (en) * | 2017-10-30 | 2019-05-07 | 彤程化学（中国）有限公司 | A kind of modified anacardol-phenol-formaldehyde resin and its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730519A (en) * | 2005-09-14 | 2006-02-08 | 北京高盟化工有限公司 | Coloured clad armor plate composite material and adhesive used thereon |
| CN102796485A (en) * | 2012-09-11 | 2012-11-28 | 无锡市万力粘合材料有限公司 | Reactive polyurethane hot-melt adhesive and preparation method thereof |
| CN103555258A (en) * | 2013-10-23 | 2014-02-05 | 上海天洋热熔胶有限公司 | Preparation method of polyester/polyether mixed system polyurethane adhesive for spinning |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730519A (en) * | 2005-09-14 | 2006-02-08 | 北京高盟化工有限公司 | Coloured clad armor plate composite material and adhesive used thereon |
| CN102796485A (en) * | 2012-09-11 | 2012-11-28 | 无锡市万力粘合材料有限公司 | Reactive polyurethane hot-melt adhesive and preparation method thereof |
| CN103555258A (en) * | 2013-10-23 | 2014-02-05 | 上海天洋热熔胶有限公司 | Preparation method of polyester/polyether mixed system polyurethane adhesive for spinning |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721697A (en) * | 2017-10-30 | 2019-05-07 | 彤程化学（中国）有限公司 | A kind of modified anacardol-phenol-formaldehyde resin and its preparation and application |
| CN109721697B (en) * | 2017-10-30 | 2021-11-02 | 彤程化学（中国）有限公司 | Modified cardanol-phenol-formaldehyde resin and preparation and application thereof |
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