CN109628034A - Twice-modified calcium carbonate and contain modified calcium carbonate epoxy dry-hang glue and preparation method - Google Patents
Twice-modified calcium carbonate and contain modified calcium carbonate epoxy dry-hang glue and preparation method Download PDFInfo
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- CN109628034A CN109628034A CN201811345774.2A CN201811345774A CN109628034A CN 109628034 A CN109628034 A CN 109628034A CN 201811345774 A CN201811345774 A CN 201811345774A CN 109628034 A CN109628034 A CN 109628034A
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The present invention relates to twice-modified pearl fillers, prepare as follows: dispersing agent being dissolved in ethyl alcohol, then by the mixed stirring of calcium carbonate that drying to constant weight, revolving speed is 80~100 revs/min；After stirring 5~10min, then 5~10min of ultrasonic disperse is carried out, is warming up to 80 DEG C and dries solvent, obtain powder；By powder investment coated sand mixer pre-heating temperature elevation to 100 DEG C, the warmed-up titanate coupling agent as molten state of property investment again keeps 10~15min of high-speed stirred, cooling discharging both secondary cladding modified calcium carbonate powder.Epoxy dry-hang glue of the present invention is to be complementary to one another by a variety of epoxy resin compounding and two kinds of means of twice-modified pearl filler so that its comprehensive performance is obviously improved.The present invention also contains the epoxy dry-hang glue of this twice-modified calcium carbonate and the preparation method of this epoxy dry-hang glue.
Description
Technical field
The present invention relates to the technical fields of epoxy dry-hang glue to contain this in particular to a kind of twice-modified pearl filler
The epoxy dry-hang glue of the twice-modified calcium carbonate of kind and the preparation method of this epoxy dry-hang glue.Epoxy dry-hang glue of the present invention be by
A variety of epoxy resin compoundings are complementary to one another with two kinds of means of twice-modified pearl filler so that its comprehensive performance obtains obviously
It is promoted.
Background technique
A branch of the epoxy construction adhesive as epoxyn, development in recent years is steady quick, especially
Epoxy dry-hang glue.As the stone material dry suspending glue for playing important bonding effect in curtain wall construction, it is widely used in curtain wall construction.
Existing dry-hang glue is largely bi-component: component A is made of bisphenol A type epoxy resin, filler and diluent；B component is by amine
Class curing agent, filler and diluent composition.There is also many urgent problems to be solved for dry-hang glue class product at present, for example, A group
Part since main body is bisphenol A epoxide resin, viscosity is very big when low temperature, and easily crystallization, these can all cause construction greatly
Inconvenience, while being driven by market interest competition, in order to save production cost to greatest extent, existing dry-hang glue filler loading is big,
Resin ratio is small, has not only been further exacerbated by the above problem, while also having large effect to product mechanical property, often up to not
To the requirement in construction structure glue JC887-2001 " dry-hang stone curtain wall epoxy adhesive ", especially impact flexibility, this is just
It is be easy to cause qualitative problems of construction, What is more, and stress cracking occurs for bonding layer, seriously affects the safety of stone curtain wall.
Traditional epoxy dry-hang glue use stearic acid modified calcium carbonate as main body fill filler, although with epoxy resin,
Curing agent has good compatibility and outer lubricating ability, in the biggish situation of loading also dry-hang glue can have good
Appearance, feel and thixotropy, but toughness of products is poor, is unable to reach requirement.
Traditional epoxy systems method for toughening, including resin modified, curing agent are composite modified, the organic toughener of addition (such as
Nitrile rubber, polyurethane, plasticizer etc.) etc., though these methods achieve certain effect, largely improves and answer
With cost, and operate it is increasingly complex, it is relatively high from the material cost used, in Patent No. CN 107699180A
Mentioned in file a kind of toughening type dry-hang glue and preparation method thereof, use nylon material and toughener, and resin and powder
Ratio is essentially 1:1, although achieving preferable impact property and bending modulus, price is more expensive.
Therefore, researching and developing the outstanding modified filler of one kind makes the comprehensive of epoxy dry-hang glue on the basis of increasing filler usage amount
The getable promotion of conjunction property, and the price for reducing epoxy dry-hang glue becomes an important and urgent job.
Summary of the invention
The first object of the present invention is to provide a kind of twice-modified pearl filler, more can be with using this filler
Product price is reduced, and there are also promoted for the comprehensive performance of epoxy dry-hang glue.
The second object of the present invention is to provide a kind of epoxy dry-hang glue containing above-mentioned twice-modified calcium carbonate, it has
Excellent combination property and feature low in cost.
The third object of the present invention is to provide the preparation method of above-mentioned epoxy dry-hang glue.
The first object of the present invention is reached by following measure: twice-modified pearl filler, which is characterized in that
It prepares as follows:
(1) dispersing agent is dissolved in ethyl alcohol, then by the mixed stirring of calcium carbonate, it is equal carries out ultrasonic disperse after stirring again
It is even, solvent is dried to obtain powder；
(2) powder preheating is heated up again, the titanate coupling agent of property investment molten state, stirring, cooling go out again
Expect the modified calcium carbonate powder to get secondary cladding；
The dispersing agent is selected from aliphatic alcohol polyoxyvinethene phosphate, thermally coupled distillation columns, triphen second
Base phenol polyoxyethylene phosphonate；
100 parts of the calcium carbonate, 0.5~1.5 part of dispersing agent, 1~3 part of coupling agent；
The coupling agent be selected from three isostearic acid isopropyl titanates, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters,
Di(dioctylpyrophosphato) ethylene titanate.
In the above-mentioned technical solutions, the calcium carbonate is the calcium carbonate of 800~2000 mesh.
In the above-mentioned technical solutions, the calcium carbonate is 1250 mesh, and the dispersing agent is 1 part, and the coupling agent is 2 parts.
The second object of the present invention is reached by following measure: special containing modified calcium carbonate epoxy dry-hang glue
Sign is: it is made of in mass ratio for 1:1 component A and B component,
The component A is made of following raw material by number: 40~50 parts of composite epoxy resin；5~15 parts of diluent；Thixotroping
1~3 part of agent；120~150 parts of modified calcium carbonate；
The B component is made of following raw material by number: 30~45 parts of pnenolic aldehyde amine hardener, 5~8 parts of diluent, being promoted
3~6 parts of agent, 120~180 parts of modified calcium carbonate；
The modified calcium carbonate is the twice-modified pearl filler.
In the above-mentioned technical solutions, the composite epoxy resin is made of following raw material by number, with total amount for 100 mass
It calculates: general bisphenol A epoxide resin E51,20~50 part；Phenolic ketone epoxy resin, 20~50 parts；Polyether-modified side chain type asphalt mixtures modified by epoxy resin
20~30 parts of rouge.
In the above-mentioned technical solutions, the composite epoxy resin is made of following raw material by number, with total amount for 100 mass
It calculates: 30 parts of general bisphenol A epoxide resin E51,50 parts of phenolic ketone epoxy resin, 20 parts of polyether-modified side chain type epoxy resin；Or
20 parts of general bisphenol A epoxide resin E51,50 parts of phenolic ketone epoxy resin, 30 parts of polyether-modified side chain type epoxy resin.
In the above-mentioned technical solutions, diluent described in component A is selected from reactive diluent benzyl glycidyl ether, C12~C14
Alkyl glycidyl ether, neopentylglycol diglycidyl ether；Diluent described in B component is benzyl alcohol.
In the above-mentioned technical solutions, the thixotropic agent is precipitated silica.
In the above-mentioned technical solutions, the promotor is selected from 2,4,6-three (dimethylamino methyl) phenol, N- aminoethyl piperazine
Piperazine.
The third object of the present invention is reached by following measure: the method for preparing above-mentioned epoxy dry-hang glue, including
Following steps:
(1) prepared by component A: by above-mentioned each component weight, reaction kettle is added in composite epoxy resin, diluent
In, stir 10 minutes under 35~50 revs/min of revolving speeds, be then added thereto thixotropic agent, adjust revolving speed to 70 revs/min, after
Continuous stirring 30 minutes adds twice-modified pearl filler, adjusts revolving speed to 50~65 revs/min, stir 30 minutes to get
To component A；
(2) prepared by B component: pressing above-mentioned each component weight, reaction kettle is added in curing agent, diluent, promotor
In, it is stirred 25 minutes under 35~50 revs/min of revolving speeds, adds twice-modified pearl filler, continue stirring 30~40 minutes,
Obtain B component.
It is prepared when use by AB component 1:1.
Compared with prior art, the present invention has the advantage that
The present invention is intended to provide a kind of low-cost mode promotes dry-hang glue comprehensive performance, it is respectively adopted two kinds of ways
Diameter realizes the purpose, is original single bisphenol-A epoxy is substituted by using a variety of epoxy resin compounded technologies first
Resin does main body, reduces the single resin purity of substance system, effectively prevents the drawbacks of low temperature easily crystallizes as a mixture,
The resin system of compounding still possesses mobility at subzero 5 DEG C, while the phenolic ketone epoxy resin price used is also slightly lower and bis-phenol
A epoxy has some superiority.On the other hand, the phenolic ketone epoxy and polyether-modified side group epoxy of introducing, due to the structure of its own
Some three officials and multi-functional epoxy group are increased, the crosslink density reacted with curing agent is improved, solidfied material can be promoted
Heat resistance.Secondly, it is twice-modified by being carried out for the calcium carbonate as filler material, original powder body is carried out first with dispersing agent
Physics coating, under the action of dispersion force, is adsorbed on calcium carbonate surface, shape by physical forces such as Van der Waals force or electrostatic force
At clad, reduce modified calcium carbonate oil factor, loading increases in organic matrix, and particle is kept to be chronically at point
Bulk state.Herein on basis, secondary cladding further is carried out to modified calcium, using the functional group in coupling agent molecule and sufficiently
The active site on the calcium carbonate powder surface after dispersion is chemically reacted, and coupling agent is made to be coated on the surface of calcium carbonate granule, is increased
The strong compatibility and dispersibility of calcium carbonate and filling organic matrix, so as to improve the processing performance and physical force of composite material
Learn performance.With the stearic acid modified calcium phase ratio largely used in existing dry-hang glue, fill it into epoxy dry-hang glue with bright
Aobvious advantage, not only product appearance is unaffected, while also greatly improving the impact strength of product.Of the invention is prepared
Cladding gum resin and powder have basically reached 1:3~4 than range, and cost price can reduce by 50% substantially, more adapt to current
Market competition market.
Specific embodiment
Below with reference to the embodiment performance that the present invention will be described in detail, but they and do not constitute a limitation of the invention,
It is only for example.Simultaneously by illustrating that advantages of the present invention will become clearer and be readily appreciated that.
Twice-modified pearl filler, prepares as follows:
(1) dispersing agent being dissolved in ethyl alcohol, then by the mixed stirring of calcium carbonate that drying to constant weight, revolving speed is 80~
100 revs/min；After stirring 5~10min, then 5~10min of ultrasonic disperse is carried out, is warming up to 80 DEG C and dries solvent, obtain powder
Material；
(2) by powder investment coated sand mixer pre-heating temperature elevation to 100 DEG C, property investment is warmed-up again becomes molten
Melt the titanate coupling agent of state, keep 10~15min of high-speed stirred, cooling discharging both secondary cladding modified calcium carbonate powder
Material, high-speed stirred revolving speed are 1000~2000 revs/min；
It should be understood that the purity of equipment and substance has difference, therefore relevant skill due to the difference of raw material producer
Art parameter, such as speed, time and temperature etc. can be varied, and should be regarded as equivalent technical solution.
The dispersing agent is selected from but is not limited only to aliphatic alcohol polyoxyvinethene phosphate, nonylphenol polyoxyethylene ether phosphoric acid
Ester, triphenoethyl benzene phenol polyethenoxy ether phosphate；
100 parts of the calcium carbonate, 0.5~1.5 part of dispersing agent, 1~3 part of coupling agent；
The coupling agent is selected from but is not limited only to three isostearic acid isopropyl titanates, (the dioctyl phosphoric acid acyl-oxygen of isopropyl three
Base) titanate esters, Di(dioctylpyrophosphato) ethylene titanate.
The calcium carbonate is the calcium carbonate of 800~2000 mesh.Mesh number it is too low it is easy sedimentation, mesh number crosses strong mechanical performance can be bright
Aobvious decline, oil factor also can be excessive.
The calcium carbonate is 1250 mesh, and the dispersing agent is 1 part, and the coupling agent is 2 parts.
Containing modified calcium carbonate epoxy dry-hang glue, it is made of in mass ratio for 1:1 component A and B component,
The component A is made of following raw material by number: 40~50 parts of composite epoxy resin；5~15 parts of diluent；Thixotroping
1~3 part of agent；120~150 parts of modified calcium carbonate；
The B component is made of following raw material by number: 30~45 parts of pnenolic aldehyde amine hardener, 5~8 parts of diluent, being promoted
3~6 parts of agent, 120~180 parts of modified calcium carbonate；
The modified calcium carbonate is the twice-modified pearl filler.
The composite epoxy resin is made of following raw material by number, with total amount for 100 Mass Calculations: general bisphenol-A ring
Oxygen resin E51,20~50 part；Phenolic ketone epoxy resin, 20~50 parts；20~30 parts of polyether-modified side chain type epoxy resin.
The composite epoxy resin is made of following raw material by number, with total amount for 100 Mass Calculations: general bisphenol-A ring
30 parts of oxygen resin E51,50 parts of phenolic ketone epoxy resin, 20 parts of polyether-modified side chain type epoxy resin；Or general bisphenol-A epoxy tree
20 parts of rouge E51,50 parts of phenolic ketone epoxy resin, 30 parts of polyether-modified side chain type epoxy resin.
Diluent described in component A is selected from but is not limited only to reactive diluent benzyl glycidyl ether, C12~C14Alkyl shrinks
Glycerin ether, neopentylglycol diglycidyl ether；Diluent described in B component is benzyl alcohol.
The thixotropic agent is selected from but is not limited only to as precipitated silica.
The promotor is selected from but is not limited only to 2,4,6-three (dimethylamino methyl) phenol, N- aminoethyl piperazine.
The phenolic ketone epoxy resin, general structure are as follows:
In formula (I), n is the integer in 2~4 ranges, and epoxide equivalent is 220~260g/mol.
In the above-mentioned technical solutions, the polyether-modified side chain type epoxy resin is (by Yueyang green hill finish Co., Ltd
There is provided), general structure is as follows:
In formula (II), R is-CH2-CH2OrN be 4~9 ranges in integer, epoxide equivalent be 400~
430g/mol。
The method for preparing above-mentioned epoxy dry-hang glue, comprising the following steps:
(1) prepared by component A: by above-mentioned each component weight, reaction kettle is added in composite epoxy resin, diluent
In, stir 10 minutes under 35~50 revs/min of revolving speeds, be then added thereto thixotropic agent, adjust revolving speed to 70 revs/min, after
Continuous stirring 30 minutes adds twice-modified pearl filler, adjusts revolving speed to 50~65 revs/min, stir 30 minutes to get
To component A；
(2) prepared by B component: pressing above-mentioned each component weight, reaction kettle is added in curing agent, diluent, promotor
In, it is stirred 25 minutes under 35~50 revs/min of revolving speeds, adds twice-modified pearl filler, continue stirring 30~40 minutes,
Obtain B component.
It is prepared when use by AB component 1:1.
First: the screening and optimizing of twice-modified calcium carbonate preparation method
1. the optimization of twice-modified pearl filler technique.To the investment of twice-modified reagent in secondary cladding preparation process
Amount optimizes.
Measuring brightness is measured referring to the universal method of GB/T 23774-2009 inorganic chemical product measuring brightness.
Oil factor test method are as follows: reagent dioctyl phthalate is gradually added in the powder of certain weight, directly
To being sufficiently stirred into bulk body, and leached without excessive reagent, to increase the oil absorption of the Mass Calculation sample of reagent, specific number
Value take make 100g powder be sufficiently stirred can at when bulk body be added reagent weight, unit g/g.
Resin body uses unified E51 epoxy resin (Yueyang petrochemical industry Co., Ltd, Ba Ling Huaxing) and T31 curing agent (nothing
Xi Qianguang Chemical Co., Ltd.) according to the ratio 3:1 solidified, after different powders is mixed in the way of 2:1 with resin, into
Row one-component sample preparation test sample tests impact flexibility, and method is tested with reference to JC887-2001 standard.Wherein blank sample is not change
The 2000 mesh calcium carbonate samples (offer of mineral products processing factory, Lingshou County Hengchang) that property is crossed.
Table 1
Originally in a certain range, with the addition of phosphate dispersant, calcium carbonate is in resin due to being dispersed
The effect of the surface-active of agent, dispersion can gradually improve, while since charge effect can keep relatively good between particle
Stability, this plays facilitation, especially needle to this twice-modified process of suspended particulate to using coupling agent
The case where being easy flocking settling in resin for calcium carbonate itself, considerably increasing can activate a little, improve activation efficiency, but
With further increasing for dispersing agent, will form micella and envelope calcium carbonate granule completely, hinder particle surface activation point with
The next step of titanate esters is reacted, and can activation grade be reduced instead, oil factor also first reduces therewith to be increased afterwards.Titanate coupling agent
Increase be conducive to increase activation grade, but simultaneously because its dosage will also result in the reduction of powder whiteness while increase,
Gu should not also add, and be limited to can reactivity site total amount influence, only before putting into suitable dispersant dose
It puts, the additive amount of activation grade and coupling agent can just show positively related rule.Relative to the unmodified calcium carbonate of blank and
The modified calcium carbonate for being only added to dispersing agent or coupling agent is compared, and twice-modified powder is shown in terms of reducing oil factor
Biggish superiority, so that colloid can still have preferable feel and thixotropy, while whiteness base in the case where larger solid-to-liquid ratio
Instinct is maintained at 93 or so, little to appearance effects, and from Mechanical Data, the powder of twice-modified mistake is substantially better than blank sample
It only have passed through the powder that dispersing agent or coupling agent one of which single were modified.
In conclusion dispersing agent additive amount accounts for powder gross mass after optimization (with modified calcium carbonate for the calculating of 100 mass parts)
Range is more appropriate in 0.5~1.5 part, and optimal is 1 part, coupling agent additive amount account for powder gross mass range in 1~3 part compared with
To be suitable, optimal is 2 parts.
Second: the optimization of component A compounding epoxy ratio
It compares with general purpose epoxy resin E51, while being solidified with B group of formula, investigate performance change, determine optimal model
It encloses.
Novel modified calcium is homemade twice-modified pearl filler in following table, and commercially available activated Calcium carbonate sample is by Lingshou
Lan Xiang mineral products processing factory, county provides.Every result of Mechanics Performance Testing presses JC887-2001 and carries out standard sample preparation and test
Obtained by data.
Only epoxy resin portion is adjusted A group of formula by following compound proportion, remaining is fixed formula rate, while with
Fixed B group of formula carries out mixing cured sample preparation, investigates the influence to mechanical property with this.
The investigation of component A epoxy resin portion difference compound proportion
Table 2
It can be seen that in different compounded formula and pure E51 general purpose epoxy resin solidfied material mechanical property comparison can be with
Find out, the increase of phenolic ketone epoxy resin ratio can also reduce impact to the integral rigidity increase effect of haveing a certain upgrade simultaneously
Toughness, it is obvious that polyether-modified side chain type epoxy resin increases system toughness, but bigger on bending elastic modulus influence, adds
Dosage is unsuitable excessively high, while from the perspective of powder, being made using homemade modified calcium due to introducing titanate coupling agent
It obtains resin system and the bonding force at inorganic interface further strengthens, drawing is cut to be promoted with compression shear numerical value, simultaneously because phenolic ketone
The compounding of epoxy resin, compensating for active powder material can frequently result in the deficiency slightly declined in bending elastic modulus.
In conclusion general bisphenol A epoxide resin E51 in component A epoxy compound system, 20~50 parts, phenolic ketone asphalt mixtures modified by epoxy resin
Rouge, 20~50 parts, 20~30 parts of polyether-modified side chain type epoxy resin (by the total amount of three kinds of epoxy resin based on 100 parts).Its
Middle proportion optimizing is that phenolic ketone epoxy resin accounts for 50 parts, and bisphenol A epoxide resin E51 and the polyether epoxy containing bisphenol-A respectively account for 20
Or 30 parts.
Embodiment 1
The preparation of twice-modified calcium carbonate
1g aliphatic alcohol polyethenoxy phosphate is dissolved in the ethyl alcohol of 40g, then by the 800 mesh calcium carbonate that drying to constant weight
The mixed stirring of 200g, revolving speed are 80 revs/min；After stirring 5min, then ultrasonic disperse 5min is carried out, is finally warming up to 80 DEG C
Solvent is dried, powder P1 is obtained.Then by powder P1 investment coated sand mixer pre-heating temperature elevation to 100 DEG C, property is thrown again
Enter three isostearic acid isopropyl titanate 2g being preheated as molten state, keep high-speed stirred 10min, cooling discharging both it is secondary
The modified calcium carbonate powder P2 of cladding.
Pnenolic aldehyde amine hardener (self-control) preparation: anacardol and mixed amine A1000 (BASF AG's production) equimolar are added
In there-necked flask, 65 DEG C are warming up to, stirring to mixed liquor is in colourless transparent solution, is added portionwise and the equimolar poly of mixed amine in 1h
Formaldehyde stirring need to control the speed that metaformaldehyde is added because of exothermic heat of reaction, until generating brown liquid, then be warming up to 80 DEG C, stir
Reaction 0.5h is mixed, vacuum dehydration discharges to arrive pnenolic aldehyde amine hardener.
Make the preparation route of curing agent routinely by oneself, self-control can guarantee the product quality, and the curing agent of outsourcing may join
Miscellaneous diluent or promotor, influence properties of product and effect.
The preparation of component A:
It takes bisphenol A epoxide resin 50g, polyether-modified side chain type epoxy resin 50g to be uniformly mixed and prepares composite epoxy resin
100g.Take 40g composite epoxy resin that 3g precipitating is added after 5g benzyl glycidyl ether is by the speed stirring 10min of 35r/min
Method silica, adjustment revolving speed to 70r/min after stirring 30min, are added modified filler (i.e. twice-modified pearl filler)
120g, adjusting revolving speed are 50r/min, stir 30min.
The preparation of B component:
Pnenolic aldehyde amine hardener 30g, 5g benzyl alcohol, 3g 2,4 are taken, 6-three (dimethylamino methyl) phenol are sufficiently mixed, and are adjusted
Section revolving speed is 35r/min, stirs 25min, adds 120g modified filler (i.e. twice-modified pearl filler), continue to stir
30min.
By above-mentioned component A and B component according to the proportion of 1:1, mixes, high-performance epoxy proposed by the invention can be obtained
Dry-hang glue.
Embodiment 2
The preparation of modified powder
2g thermally coupled distillation columns are dissolved in the ethyl alcohol of 40g, then by the 1250 mesh carbon that drying to constant weight
The sour mixed stirring of calcium 200g, revolving speed 90r/min；After stirring 7min, then ultrasonic disperse 8min is carried out, is finally warming up to 80
DEG C solvent is dried, obtains powder P1.Then by powder P1 investment coated sand mixer pre-heating temperature elevation to 100 DEG C, property again
Warmed-up isopropyl three (dioctyl phosphoric acid acyloxy) the titanate esters 4g as molten state of investment, keeps high-speed stirred 12min, cold
But discharge both secondary cladding modified calcium carbonate powder P2.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1
The preparation of component A
It takes bisphenol A epoxide resin 50g, phenolic ketone epoxy resin 50g to be uniformly mixed and prepares composite epoxy resin 100g.Take 45g
Composite epoxy resin, 10g C12~C14After stirring 10min by the speed of 40r/min, 2g precipitating is added in fatty glycidyl ether
After stirring 30min, modified filler 135g is added in method silica, adjustment revolving speed to 70r/min, and adjusting revolving speed is 60r/min,
Stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 40g, 6.5g benzyl alcohol is taken, 4.5g N- aminoethyl piperazine is sufficiently mixed, and adjusts revolving speed
For 45r/min, 25min is stirred, 160g modified filler is added, continues to stir 35min.
By above-mentioned component A and B component according to the proportion of 1:1, mixes, high-performance epoxy proposed by the invention can be obtained
Dry-hang glue.
Embodiment 3
The preparation of modified powder
3g triphenoethyl benzene phenol polyethenoxy ether phosphate is dissolved in the ethyl alcohol of 40g, then by drying to constant weight
The 2000 mixed stirrings of mesh calcium carbonate 200g, revolving speed 100r/min；After stirring 10min, then ultrasonic disperse 10min is carried out,
It is finally warming up to 80 DEG C to dry solvent, obtains powder P1.Then powder P1 is put into coated sand mixer pre-heating temperature elevation to 100
DEG C, warmed-up isopropyl three (dioctyl phosphoric acid acyloxy) the titanate esters 6g as molten state of property investment, keeps high speed again
Stir 15min, cooling discharging both secondary cladding modified calcium carbonate powder P2.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1
The preparation of component A
Take bisphenol A epoxide resin E51,30g, phenolic ketone epoxy resin 50g, polyether-modified side chain type epoxy resin 20g mixing
Uniformly, composite epoxy resin 100g is prepared.50g composite epoxy resin is taken, 15g neopentylglycol diglycidyl ether presses 40r/min
Speed stirring 10min after, 1g precipitated silica is added, adjustment revolving speed is to 70r/min, after stirring 30min, is added and is modified
Filler 150g, adjusting revolving speed are 65r/min, stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 45g, 8g benzyl alcohol is taken, 6g N- aminoethyl piperazine is sufficiently mixed, and is adjusted revolving speed and is
50r/min stirs 25min, adds 180g modified filler, continues to stir 40min.
By above-mentioned component A and B component according to the proportion of 1:1, mixes, high-performance epoxy proposed by the invention can be obtained
Dry-hang glue.
Embodiment 4
The preparation of modified powder
2g triphenoethyl benzene phenol polyethenoxy ether phosphate is dissolved in the ethyl alcohol of 40g, then by drying to constant weight
The 1250 mixed stirrings of mesh calcium carbonate 200g, revolving speed 85r/min；After stirring 10min, then ultrasonic disperse 8min is carried out, most
After be warming up to 80 DEG C and dry solvent, obtain powder P1.Then powder P1 is put into coated sand mixer pre-heating temperature elevation to 100
DEG C, the warmed-up three isostearic acid isopropyl titanate 4g as molten state of property investment, keep high-speed stirred 12min again, cold
But discharge both secondary cladding modified calcium carbonate powder P2.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1
The preparation of component A
Take bisphenol A epoxide resin 20g, phenolic ketone epoxy resin 50g, polyether-modified side chain type epoxy resin 30g uniformly mixed,
Prepare composite epoxy resin 100g.45g composite epoxy resin is taken, 8g neopentylglycol diglycidyl ether presses the speed of 50r/min
After stirring 10min, 1.5g precipitated silica is added, after stirring 30min, modified filler is added in adjustment revolving speed to 70r/min
145g, adjusting revolving speed are 60r/min, stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 40g, 6g benzyl alcohol is taken, 5g N- aminoethyl piperazine is sufficiently mixed, and is adjusted revolving speed and is
50r/min stirs 25min, adds 175g modified filler, continues to stir 35min.
By above-mentioned component A and B component according to the proportion of 1:1, mixes, high-performance epoxy proposed by the invention can be obtained
Dry-hang glue.
Embodiment 5
The preparation of modified powder
1g thermally coupled distillation columns are dissolved in the ethyl alcohol of 40g, then by the 1250 mesh carbon that drying to constant weight
The sour mixed stirring of calcium 200g, revolving speed 72r/min；After stirring 10min, then ultrasonic disperse 5min is carried out, is finally warming up to
80 DEG C dry solvent, obtain powder P1.Then by powder P1 investment coated sand mixer pre-heating temperature elevation to 100 DEG C, again
Property the warmed-up three isostearic acid isopropyl titanate 6g as molten state of investment, keep high-speed stirred 12min, cooling discharging is both
The modified calcium carbonate powder P2 of secondary cladding.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1
The preparation of component A
Take bisphenol A epoxide resin 30g, phenolic ketone epoxy resin 50g, polyether-modified side chain type epoxy resin 20g uniformly mixed,
Prepare composite epoxy resin 100g.50g composite epoxy resin is taken, 12g neopentylglycol diglycidyl ether presses the speed of 35r/min
After stirring 10min, 2g precipitated silica is added, after stirring 30min, modified filler is added in adjustment revolving speed to 70r/min
140g, adjusting revolving speed are 50r/min, stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 45g, 5g benzyl alcohol, 5g 2,4 are taken, 6-three (dimethylamino methyl) phenol sufficiently mix
It closes, adjusting revolving speed is 40r/min, stirs 25min, adds 170g modified filler, continues to stir 35min.
By above-mentioned component A and B component according to the proportion of 1:1, mixes, high-performance epoxy proposed by the invention can be obtained
Dry-hang glue.
Embodiment 6
The preparation of modified powder:
3g aliphatic alcohol polyethenoxy phosphate is dissolved in the ethyl alcohol of 40g, then by the 800 mesh calcium carbonate that drying to constant weight
The mixed stirring of 200g, revolving speed 80r/min；After stirring 8min, then ultrasonic disperse 10min is carried out, is finally warming up to 80 DEG C
Solvent is dried, powder P1 is obtained.Then by powder P1 investment coated sand mixer pre-heating temperature elevation to 100 DEG C, property is thrown again
Enter three isostearic acid isopropyl titanate 2.5g being preheated as molten state, keep high-speed stirred 10min, cooling discharging both obtains two
The modified calcium carbonate powder P2 of secondary cladding.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1.
The preparation of component A
Take bisphenol A epoxide resin 50g, phenolic ketone epoxy resin 30g, polyether-modified side chain type epoxy resin 20g uniformly mixed,
Prepare composite epoxy resin 100g.50g composite epoxy resin is taken, 6.5g neopentylglycol diglycidyl ether presses the speed of 40r/min
After degree stirring 10min, 1g precipitated silica is added, after stirring 30min, modified filler is added in adjustment revolving speed to 70r/min
145g, adjusting revolving speed are 55r/min, stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 45g, 5.5g benzyl alcohol is taken, 4g N- aminoethyl piperazine is sufficiently mixed, and is adjusted revolving speed and is
38r/min stirs 25min, adds 175g modified filler, continues to stir 40min.
By above-mentioned component A and B component according to the proportion of 1:1, mixes, high-performance epoxy proposed by the invention can be obtained
Dry-hang glue.
Embodiment 7
The preparation of modified powder
2g triphenoethyl benzene phenol polyethenoxy ether phosphate is dissolved in the ethyl alcohol of 40g, then by drying to constant weight
The 1250 mixed stirrings of mesh calcium carbonate 200g, revolving speed 85r/min；After stirring 10min, then ultrasonic disperse 8min is carried out, most
After be warming up to 80 DEG C and dry solvent, obtain powder P1.Then powder P1 is put into coated sand mixer pre-heating temperature elevation to 100
DEG C, the warmed-up Di(dioctylpyrophosphato) ethylene titanate 4g as molten state of property investment, keeps high speed again
Stir 10min, cooling discharging both secondary cladding modified calcium carbonate powder P2.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1
The preparation of component A
Take bisphenol A epoxide resin 50g, phenolic ketone epoxy resin 20g, polyether-modified side chain type epoxy resin 30g uniformly mixed,
Prepare composite epoxy resin 100g.45g composite epoxy resin is taken, 5g benzyl glycidyl ether is stirred by the speed of 40r/min
After 10min, 1.5g precipitated silica is added, after stirring 30min, modified filler is added in adjustment revolving speed to 70r/min
150g, adjusting revolving speed are 65r/min, stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 35g, 5g benzyl alcohol is taken, 4g N- aminoethyl piperazine is sufficiently mixed, and is adjusted revolving speed and is
42r/min stirs 25min, adds 180g modified filler, continues to stir 35min.
By above-mentioned component A and B component according to the proportion of 1:1, mixes, high-performance epoxy proposed by the invention can be obtained
Dry-hang glue.
Embodiment 8
The preparation of modified powder
3g triphenoethyl benzene phenol polyethenoxy ether phosphate is dissolved in the ethyl alcohol of 40g, then by drying to constant weight 800
The mixed stirring of mesh calcium carbonate 200g, revolving speed 95r/min；After stirring 10min, then ultrasonic disperse 10min is carried out, finally risen
Temperature dries solvent to 80 DEG C, obtains powder P1.Then by powder P1 investment coated sand mixer pre-heating temperature elevation to 100 DEG C, then
The disposable warmed-up three isostearic acid isopropyl titanate 5g as molten state of investment, keep high-speed stirred 10min, cooling discharging
Both secondary cladding modified calcium carbonate powder P2.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1
The preparation of component A
Take bisphenol A epoxide resin 35g, phenolic ketone epoxy resin 40g, polyether-modified side chain type epoxy resin 25g uniformly mixed,
Prepare composite epoxy resin 100g.40g composite epoxy resin is taken, 12g benzyl glycidyl ether is stirred by the speed of 45r/min
After 10min, 2.5g precipitated silica is added, after stirring 30min, modified filler is added in adjustment revolving speed to 70r/min
145g, adjusting revolving speed are 60r/min, stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 40g, 7g benzyl alcohol is taken, 5g N- aminoethyl piperazine is sufficiently mixed, and is adjusted revolving speed and is
46r/min stirs 25min, adds 175g modified filler, continues to stir 35min.By above-mentioned component A and B component according to
The proportion of 1:1, mixing, can be obtained high-performance epoxy dry-hang glue proposed by the invention.
Comparative example
Powder directly takes commercially available common active calcium carbonate (about 1250 mesh) to be provided by mineral products processing factory, Lingshou County Hengchang.
The preparation of pnenolic aldehyde amine hardener is the same as embodiment 1
The preparation of component A
Take the universal bisphenol A epoxide resin E51 of 50g, 6.5g C12~C14Fatty glycidyl ether presses the speed of 40r/min
After stirring 12min, 2g precipitated silica is added, after stirring 30min, active carbon is added in adjustment revolving speed to 65r/min
Sour calcium 150g, adjusting revolving speed are 50r/min, stir 30min.
The preparation of B component
Pnenolic aldehyde amine hardener (self-control) 45g, 5g benzyl alcohol, 4g 2,4 are taken, 6-three (dimethylamino methyl) phenol sufficiently mix
It closes, adjusting revolving speed is 35r/min, stirs 25min, adds 170g common active calcium carbonate, continues to stir 35min.
Above-mentioned component A is mixed with B component according to the proportion of 1:1, as uses dry-hang glue as a comparison.
Above-described embodiment compares ratio data and increases as can be seen from the above table, is especially guaranteeing bending elastic modulus
In the case where remaining unchanged, On Impact Toughness is promoted obviously, simultaneously because introducing the phenolic ketone epoxy resin of polyfunctionality
Reason, heat resistance is also obviously improved, and wherein embodiment 4 is comprehensive performance optimal set.
Other unspecified parts are the prior art, are retouched in detail although above-described embodiment has made the present invention
It states, but it is only a part of the embodiments of the present invention, rather than all.Field technical staff can also be according to the present embodiment
Other embodiments are obtained under the premise of not inventively, these belong to the scope of the present invention.
Claims (10)
1. twice-modified pearl filler, which is characterized in that prepare as follows:
(1) dispersing agent being dissolved in ethyl alcohol, then by the mixed stirring of calcium carbonate, it is uniform to carry out ultrasonic disperse after stirring again,
Solvent is dried to obtain powder；
(2) powder preheating is heated up again, again the titanate coupling agent of property investment molten state, stirring, cooling discharging, i.e.,
Obtain the modified calcium carbonate powder of secondary cladding；
The dispersing agent is selected from aliphatic alcohol polyoxyvinethene phosphate, thermally coupled distillation columns, triphenoethyl benzene
Phenol polyethenoxy ether phosphate；
100 parts of the calcium carbonate, 0.5~1.5 part of dispersing agent, 1~3 part of coupling agent；
The coupling agent is selected from three isostearic acid isopropyl titanates, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, bis- (two
Octyloxy pyrophosphoric acid ester group) ethylene titanate esters.
2. twice-modified pearl filler according to claim 1, it is characterised in that the calcium carbonate is 800~2000 mesh
Calcium carbonate.
3. twice-modified pearl filler according to claim 1 or 2, it is characterised in that the calcium carbonate is 1250 mesh,
The dispersing agent is 1 part, and the coupling agent is 2 parts.
4. containing modified calcium carbonate epoxy dry-hang glue, it is characterised in that: it is made of in mass ratio for 1:1 component A and B component,
The component A is made of following raw material by number: 40~50 parts of composite epoxy resin；5~15 parts of diluent；Thixotropic agent 1
~3 parts；120~150 parts of modified calcium carbonate；
The B component is made of following raw material by number: 30~45 parts of pnenolic aldehyde amine hardener, 5~8 parts of diluent, promotor 3~
6 parts, 120~180 parts of modified calcium carbonate；
The modified calcium carbonate is twice-modified pearl filler described in any claim in claim 1-3.
5. described in claim 4 contain modified calcium carbonate epoxy dry-hang glue, it is characterised in that: the composite epoxy resin by
Following raw material is formed by number, is that 100 mass parts calculate: general bisphenol A epoxide resin E51 with total amount, and 20~50 parts；Phenolic ketone ring
Oxygen resin, 20~50 parts；20~30 parts of polyether-modified side chain type epoxy resin.
6. described in claim 4 contain modified calcium carbonate epoxy dry-hang glue, it is characterised in that: the composite epoxy resin by
Following raw material is formed by number, is 100 mass parts calculating: 30 parts of general bisphenol A epoxide resin E51, phenolic ketone asphalt mixtures modified by epoxy resin with total amount
50 parts of rouge, 20 parts of polyether-modified side chain type epoxy resin；Or general 20 parts of bisphenol A epoxide resin E51, phenolic ketone epoxy resin 50
Part, 30 parts of polyether-modified side chain type epoxy resin.
7. containing modified calcium carbonate epoxy dry-hang glue described in claim 4, it is characterised in that: the choosing of diluent described in component A
From reactive diluent benzyl glycidyl ether, C12~C14Alkyl glycidyl ether, neopentylglycol diglycidyl ether；B component institute
Stating diluent is benzyl alcohol.
8. containing modified calcium carbonate epoxy dry-hang glue described in claim 4, it is characterised in that: the thixotropic agent is the precipitation method
Silica.
9. containing modified calcium carbonate epoxy dry-hang glue described in claim 4, it is characterised in that: the promotor is selected from 2,4,
6-three (dimethylamino methyl) phenol, N- aminoethyl piperazine.
10. the method for preparing epoxy dry-hang glue described in any claim in claim 4-9, it is characterised in that including walking as follows
It is rapid:
(1) prepared by component A: pressing each component weight, composite epoxy resin, diluent is added in reaction kettle, 35~50
It stirs 10 minutes under rev/min revolving speed, is then added thereto thixotropic agent, adjust revolving speed to 70 revs/min, continue 30 points of stirring
Clock adds modified calcium carbonate, adjusts revolving speed to 50~65 revs/min, stirs 30 minutes to get component A is arrived；
(2) prepared by B component: pressing each component weight, curing agent, diluent, promotor is added in reaction kettle, 35~50
It is stirred 25 minutes under rev/min revolving speed, adds modified calcium carbonate, continue stirring 30~40 minutes, obtain B component.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016227A (en) * | 2019-05-05 | 2019-07-16 | 合肥工业大学 | A kind of nylon composite materials and preparation method thereof containing secondary surface modifying stuffing |
| CN112391138A (en) * | 2020-11-06 | 2021-02-23 | 福建省高镖建材有限公司 | Epoxy dry-hanging adhesive and preparation method thereof |
| CN116731397A (en) * | 2023-07-20 | 2023-09-12 | 浙江钦堂钙业有限公司 | Modified shell-core structure calcium carbonate with flame retardant function |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003034760A (en) * | 2001-05-18 | 2003-02-07 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate heavy and method for producing the same, and resin composition containing surface-treated calcium carbonate heavy |
| US20070293603A1 (en) * | 2006-06-19 | 2007-12-20 | Ashland Licensing And Intellectual Property Llc | Epoxy adhesive composition and use thereof |
| CN101318684A (en) * | 2008-06-28 | 2008-12-10 | 福建省万旗非金属材料有限公司 | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation |
| KR20130048878A (en) * | 2011-11-03 | 2013-05-13 | 주식회사 유니테크 | Composition for tape type collisional structural adhesives |
| CN104673163A (en) * | 2015-03-23 | 2015-06-03 | 广州市白云化工实业有限公司 | Epoxy stone dry hanging adhesive rapidly solidified at normal temperature and preparation method of epoxy stone dry hanging adhesive |
| CN104745133A (en) * | 2015-03-24 | 2015-07-01 | 王传广 | Flip chip bottom filling adhesive with normal temperature rapid capillary fluidity and rapid repairability |
| CN105085867A (en) * | 2015-09-25 | 2015-11-25 | 南通星辰合成材料有限公司 | Method for synthesizing phenolic ketone epoxy resin through solvent |
-
2018
- 2018-11-13 CN CN201811345774.2A patent/CN109628034B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003034760A (en) * | 2001-05-18 | 2003-02-07 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate heavy and method for producing the same, and resin composition containing surface-treated calcium carbonate heavy |
| US20070293603A1 (en) * | 2006-06-19 | 2007-12-20 | Ashland Licensing And Intellectual Property Llc | Epoxy adhesive composition and use thereof |
| CN101318684A (en) * | 2008-06-28 | 2008-12-10 | 福建省万旗非金属材料有限公司 | Method for preparing ultra-fine active nano-calcium carbonate with low-ore grade limestone wet-process activation |
| KR20130048878A (en) * | 2011-11-03 | 2013-05-13 | 주식회사 유니테크 | Composition for tape type collisional structural adhesives |
| CN104673163A (en) * | 2015-03-23 | 2015-06-03 | 广州市白云化工实业有限公司 | Epoxy stone dry hanging adhesive rapidly solidified at normal temperature and preparation method of epoxy stone dry hanging adhesive |
| CN104745133A (en) * | 2015-03-24 | 2015-07-01 | 王传广 | Flip chip bottom filling adhesive with normal temperature rapid capillary fluidity and rapid repairability |
| CN105085867A (en) * | 2015-09-25 | 2015-11-25 | 南通星辰合成材料有限公司 | Method for synthesizing phenolic ketone epoxy resin through solvent |
Non-Patent Citations (7)
| Title |
|---|
| MING-QIU ZHANG 等: "PERFORMANCE IMPROVEMENT OF POLYMERS BY THE ADDITION OF GRAFTED NANO-INORGANIC PARTICLES", 《CHINESE JOURNAL OF POLYMER SCIENCE》 * |
| 余锡宾 等: "ACS改性碳酸钙的应用研究", 《中外技术情报》 * |
| 吴培熙 等: "《聚合物共混改性》", 31 August 2017, 中国轻工业出版社 * |
| 张东兴 等: "《聚合物基复合材料科学与工程》", 31 July 2018, 哈尔滨工业大学出版社 * |
| 李福志: "酚酮环氧树脂的性状特征及在建筑结构胶中的应用", 《2017年第九届中国建筑胶粘剂发展论坛》 * |
| 王中平 等: "《表面物理化学》", 30 September 2015, 同济大学出版社 * |
| 郑水林 等: "《粉体表面改性》", 30 September 2011, 中国建材工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110016227A (en) * | 2019-05-05 | 2019-07-16 | 合肥工业大学 | A kind of nylon composite materials and preparation method thereof containing secondary surface modifying stuffing |
| CN110016227B (en) * | 2019-05-05 | 2021-06-04 | 合肥工业大学 | Nylon composite material containing secondary surface modified filler and preparation method thereof |
| CN112391138A (en) * | 2020-11-06 | 2021-02-23 | 福建省高镖建材有限公司 | Epoxy dry-hanging adhesive and preparation method thereof |
| CN116731397A (en) * | 2023-07-20 | 2023-09-12 | 浙江钦堂钙业有限公司 | Modified shell-core structure calcium carbonate with flame retardant function |
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