CN107523261B - A method of preparing hot melt adhesive - Google Patents
A method of preparing hot melt adhesive Download PDFInfo
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- CN107523261B CN107523261B CN201710444642.4A CN201710444642A CN107523261B CN 107523261 B CN107523261 B CN 107523261B CN 201710444642 A CN201710444642 A CN 201710444642A CN 107523261 B CN107523261 B CN 107523261B
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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
- C09J191/00—Adhesives based on oils, fats or waxes; Adhesives based on derivatives thereof
- C09J191/06—Waxes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/36—Recovery of petroleum waxes from other compositions containing oil in minor proportions, from concentrates or from residues; De-oiling, sweating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of methods for preparing hot melt adhesive.Using suitable microwax as raw material in the present invention, on the basis of common sweating process, sweating raw material is formed to stable micro-bubble in wax layer under the action of bubble stabilizer to form the channel of discharge oil, promote the quick discharge of liquid composition；Proper temperature in temperature-fall period increases the high temperature constant temperature stage, and liquid composition is carried out by wax layer using air-flow in sweating effort, the separating effect of solid-state, liquid composition is enhanced, so that sweating method can prepare the hot melt adhesive viscosity modifier of low oil content.Viscosity modifier is hot melt adhesive product after deploying again with basic resin, tackifying resin and antioxidant.The method of the present invention has many advantages, such as that investment of production equipment is low, production process is simple and operating cost is low, safety, energy conservation and solvent-free pollution and dust emission, hot melt adhesive product have curing time short, heat-resist.
Description
Technical field
The invention belongs to adhesive producing technical fields, more particularly to a kind of method for preparing hot melt adhesive.
Background technique
Hot melt adhesive is a kind of adhesive of plasticity, its physical state changes with temperature and changed in certain temperature range
Become, and chemical characteristic is constant, it is non-toxic and tasteless, belong to environmentally friendly chemicals；Product is solid, convenient for packaging, transport, storage, together
When have many advantages, such as simple production process, sizing is convenient, adhesive strength is big, speed is fast, thus is answered extensively in many fields
With.
With EVA(ethylene-vinyl acetate random copolymer) etc. elastomers be that the hot melt adhesive of basic resin is referred to as EVA hot melt
Glue is most important kind in hot melt adhesive, by basic resin, tackifying resin, viscosity modifier and antioxidant etc. at being grouped as.Base
The ratio, quality of this resin determine the basic performance (cementitiousness, melting temperature and the adhesion strength of such as glue) of hot melt adhesive.Increase
The mobility of colloid and the wetability to adherend can be improved in viscosity resin, improves adhesive property, reaches required adhesion strength.
The effect of viscosity modifier is the mobility for increasing colloid molten state, adjusts setting rate, to reach the mesh being quickly firmly bonded
's.Viscosity modifier is typically chosen paraffin, microwax, synthetic wax etc..Antioxidant is the mistake senilism of EVA hot-melt adhesive in order to prevent
Change, it is ensured that adhesive property does not change under the high temperature conditions.
The viscosity and mobility and sizability of hot melt adhesive are closely related.It is viscous that it is maximum, which to be glued viscosity influence, to hot melt adhesive
Spend regulator, i.e. wax.Because wax is the smallest ingredient of hot melt adhesive medium viscosity, hot melt adhesive is can be significantly reduced in the dosage for increasing wax
Viscosity increases its mobility.The hot melt adhesive of certain specific uses, such as the aluminum foil sealing of medicine, food, cosmetics, pesticide, machine oil
Mouthful gasket hot melt adhesive, it is of less demanding to curing time and adhesive strength, but need relatively low sizing temperature, preferable tough
Property and heat resistance.For this requirement, it is possible to reduce can meet in the case where basic resin and tackifying resin dosage to solid
The requirement for changing time and adhesive strength simultaneously reduces production cost, but to viscosity modifier when is more demanding, that is, needs using drip melt
O'clock 80 DEG C~88 DEG C, oil content be not more than 1.0%(mass content), (100 DEG C) of kinematic viscosity be not less than 10 mm2The crystallite of/s
Wax.
Microwax is one kind of pertroleum wax, be decompression residuum after propane equal solvent depitching again through dewaxing, de-oiling, purification
It is produced with molding, generally by C30~C60Isoparaffin and a small amount of n-alkane, cycloalkane composition, have under solid-state
Have than other pertroleum waxes, such as soap manufacturing paraffin and paraffin, more tiny needle-like crystal structure.The crystallite wax product standardized in national standard
Dropping point be 67 DEG C~92 DEG C, oil content be 5.0% or less.The oil content of the microwax of domestic production at present is usually 1.5%
Between~3.5%, it is not able to satisfy the requirement of aluminum foil seal gasket hot melt adhesive.
In pertroleum wax production process, dewaxing is that the slack wax that oil content is 10~30% or so is prepared by raw material of crude oil fractions
Process.De-oiling is that the process of the base oil wax below of oil content 5% is prepared using slack wax as raw material, and de-oiling technique mainly has solvent
De-oiling and sweating de-oiling.Through clay-filtered or hydrofinishing and molding, packaging and other steps, commodity stone can be obtained again in base oil wax
Oily wax.
Solvent deoiling method is according to wax and oil in selective solvent (acetone, benzene and toluene mixture；Or acetone, toluene；
Or methyl ethyl ketone, toluene) in the property of different solubility separated.Solvent deoiling technique with production process, receive by continuous, wax
Rate is high, finished product wax oil content can very low, lower production costs the advantages that, be the mainstream of current large-scale production petroleum paraffin product
De-oiling technique.But solvent deoiling technique investment of production equipment is big；It needs largely to use solvent in production process, recycling design needs
Consume a large amount of energy；Contain benzene homologues in solvent, environment can be impacted；Solvent is inflammable, be easy to cause production accident.
Sweating de-oiling method is separated using wax and oil property with different melting points.Point of various hydro carbons in pertroleum wax
Son amount Bu Tong can all make its fusing point different with structure.When being all n-alkane structure, the biggish n-alkane of molecular weight melts
Point is higher, and the fusing point of the lesser n-alkane of molecular weight is lower；When molecular weight is identical, the fusing point of isoparaffin and cycloalkane is wanted
Lower than n-alkane, and isomery degree more high-melting-point is lower, or even is at normal temperature just in liquid condition, i.e., usually said
Oil.Sweating de-oiling method does not use solvent in process of production, and only need for raw material to be heated in production process fusing point with
On temperature.
Common sweating process mainly comprises the steps that (1) preparation: pad water is (with water full of sweatbox ware plate
Lower space) charge (raw material is heated to being packed into sweatbox when fusing point or more is in a liquid state) afterwards；(2) it crystallizes: by raw material with little
10 DEG C~20 DEG C of its fusing point or less are progressively cooled in the rate of temperature fall of 4 DEG C/h.In cooling procedure, various components by fusing point by
High to Low sequence successively crystallizes and forms solid；(3) it sweating: after wax layer temperature reaches preset cooling final temperature, puts
Fall to pad water；Raw material is slowly heated to preset sweating final temperature again.In sweating effort, various components are by fusing point by low
Successively be fused into liquid to high sequence and flow out the wax layer residue (on wax) finally obtained (under wax) be exactly high-melting-point, it is low
The wax of oil-containing；(4) it refines: collecting crude product and (continue to increase temperature after sweating effort, be taken out on wax with fusing, as slightly
Product), through clay-filtered (it be warming up to predetermined temperature after melting crude product, carclazyte is added and constant temperature was stirred to the predetermined time
Filtering) after, reshaping, packaging are purpose product.
Common sweating process can produce fusing point in 40 DEG C~60 DEG C of soap manufacturing paraffin and low melt point paraffin, cannot produce drip melt
O'clock in 70 DEG C or more of crystallite wax product.Have experiments have shown that, common sweating de-oiling technique production dropping point is micro- at 70 DEG C or more
When brilliant wax product, even if using the side for extending sweating sessions (heating rate for reducing the sweating stage) and improving sweating final temperature
Method cannot still be such that solids fraction (higher melting-point wax) and liquid composition (lower melting-point wax and oil) separates well, this table
Now unrelated with yield for the oil content on sweating later period wax, i.e., the oil content on wax does not decline with the decline of yield, so general
Logical sweating de-oiling technique cannot produce crystallite wax product of the dropping point at 70 DEG C or more.
Compared with solvent deoiling, sweating de-oiling technique is intermittently operated, and product yield is lower, the production cycle is longer, but
Be sweating de-oiling technique have small investment, production process is simple, operating cost is low, production process is safe, it is energy saving and to environment without
The advantages that pollution, still has part of the manufacturer producing soap manufacturing paraffin product using this method at present.
For many years, sweating method has obtained some development in production equipment and process aspect, such as CN89214332(vertical type square
Shape multipul sections spacer diaphoresis tank), CN94223980.6(ware type sudorific device), CN98233254.8(Paraffin sweating pot),
CN200920033500.X(novel paraffin sweating tank), a kind of Efficient paraffin sweatbox of CN201210508905.0(),
CN201320127680.4(tubular type paraffin deoiler) etc., it is improved in sweating production equipment；CN91206202(is a kind of
High-efficient sweat pot for paraffin wax) improved on sweating process, but these methods there are still product yields lower, production cycle compared with
The disadvantages of long, and cannot still produce microwax.
Sweating de-oiling technique is the unique solvent-free separation method being currently known for commercial scale petroleum paraffin product,
In the today for advocating green low-carbon, environmental protection and energy saving, using sweating de-oiling technique production hot melt adhesive microwax and then aluminium foil is prepared
The demand of seal gasket hot melt adhesive is more urgent.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of method for preparing hot melt adhesive.It is specifically micro- with commodity
Brilliant wax is that sweating raw material is preferably mixed gas under the action of bubble stabilizer on the basis of common sweating process by raw material
And stable micro-bubble is formed in wax layer, be conducive to the discharge of sweating stage liquid component；It is sharp in sweating effort simultaneously
Separation solids fraction and liquid composition are forced by wax layer with air-flow, are enhanced separating effect and are accelerated separating rate；And
In the constant temperature stage for increasing crystallization and sweating effort, this solvent-free de-oiling method of sweating is allow to produce the hot melt adhesive of low oil content
Use viscosity modifier；Viscosity modifier is hot melt adhesive product after deploying again with basic resin, tackifying resin and antioxidant.This hair
Bright method has that investment of production equipment is low, production process is simple and operating cost is low, safety, energy conservation and solvent-free pollution and dust
Discharge, hot melt adhesive product have curing time short, heat-resist.
A kind of method preparing hot melt adhesive of the invention, including the following contents:
(A) sweating
(1) it preparation: using the commodity microwax that dropping point is 75 DEG C~85 DEG C as sweating raw material, is added after heating fusing
Bubble stabilizer is passed through gas under stiring and is packed into sweatbox after forming stable micro-bubble；
(2) crystallize: with 1.0 DEG C/h~3.0 DEG C/h rate by wax layer be cooled to sweating raw material dropping point~dropping point+
4.0 DEG C and high temperature constant temperature are for a period of time；5 DEG C of sweating raw material dropping point or less is cooled to 0.5 DEG C/h~2.5 DEG C/h rate again
~20 DEG C of predetermined temperature and cryogenic thermostat is for a period of time；
(3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；After wax layer reaches predetermined temperature and constant temperature for a period of time
Stop sweating；Wax layer is forced air flow through in sweating effort；
(4) it refines: being hot melt adhesive viscosity modifier after refining on wax；
(B) it deploys: viscosity modifier prepared by step (4) is melted in proportion with basic resin, tackifying resin and antioxidant
Melt and is uniformly mixed as hot melt adhesive product.
In method of the invention, the dropping point of the source commodity microwax is 75 DEG C~85 DEG C, oil content is 1.0%~
5.0%(mass content).
In method of the invention, sweating raw material is passed through gas in the presence of bubble stabilizer, stirring forms stable micro-
Sweating is carried out after minute bubbles.Bubble stabilizer described in step (1) is selected from nonionic surface active agent, anionic surface is lived
One or more of property agent, cationic surface active agent, amphoteric surfactant.The freezing point of surfactant is molten
Point is lower than the maximum temperature (i.e. predetermined temperature described in step (3)) of step (3) sweating.
Wherein, it is stearic to be selected from sorbitan monooleate, anhydrous sorbitol list for the nonionic surface active agent
Acid esters, diethylene glycol aliphatic ester, diethylene glycol monolaurate, sorbitan monopalmitate, tetraethylene glycol list are stearic
One group of substance that acid esters, polyoxypropylene stearate, sorbitan mono-laurate, polyoxyethylene fatty acid ester are constituted；Yin
Ionic surfactant is selected from fatty alcohol sulfate monoethanolamine salt, pareth sulfate, oleamide yl carboxylic acid
Sodium, sodium alkyl benzene sulfonate, N- methyl oleoyl taurate, sodium butylnaphthalenesulfonate, Disodium sulfosuccinate, suitable succinate monoester
One group of substance that sodium sulfonate is constituted.The cationic surface active agent is selected from benzyl quaternary ammonium salt, dodecyl dimethyl benzyl
Ammonium chloride, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyltrimethylammonium chloride, three second
One group of substance that amide oleate is constituted；Amphoteric surfactant is selected from empgen BB, dodecyl dimethyl oxygen
Change ammonium, aliphatic group imidazolidine derivatives, alkyl imidazoline derivatives, derivative of fatty acid, amphoteric modified epoxy ethane to add
The one group of substance constituted at object.
In method of the invention, the bubble stabilizer is preferably nonionic surface active agent, anionic surface
One group of substance that activating agent and cationic surface active agent mixing are constituted.The HLB value of bubble stabilizer is 4~10, preferably 6
~8.The additional amount of the bubble stabilizer is the 0.01%~10.0% of sweating material quality, preferably 0.1%~2.0%；
In method of the invention, gas as described in step (1) can be stable times of chemical property under the conditions of sweating
Will and spirit body, is preferably easy to get and one or more of the air of nontoxic no special odor, carbon dioxide, nitrogen.Mixed gas
Account for the 2%~20% of sweating raw material volume, preferably 5%~10%.
In method of the invention, stirring as described in step (1) can use colloid mill or other mechanical device.It is described to stir
The revolving speed mixed be 500~10000 r/min, preferably 1000~8000 r/min, with generated in sweating raw material it is uniform, tiny,
Stable foam.
In method of the invention, time of high-temperature constant temperature section described in step (2) is 0.1~6.0 hour, preferably 0.5
~5.0 hours, more preferably 1.0~4.0 hours；The cooling final temperature be preferably 8 DEG C of paraffin dropping point or less~
15℃；The time of the cryogenic thermostat is 0.1~5.0h, preferably 0.5~3.0h.
In method of the invention, the preferred sweating ware of the sweatbox, and in wax layer pressurizing device added above and/or
Increase vacuum plant below wax layer, to make wax layer form pressure difference up and down during step (3).The pressure air-flow
It is used by wax layer and increases pressure (air pressure) above wax layer and/or reduce pressure (air pressure) below wax layer, keep wax layer upper and lower
Side (side) forms pressure difference and realizes.The pressure difference is generally 0.1~5.0 atmospheric pressure, preferably 0.2~2.0 atmosphere
Pressure, to force air flow through wax layer.
In method of the invention, the predetermined temperature (i.e. final temperature) of heating described in step (3) is purpose product drip melt
- 10 DEG C of point~-1 DEG C of dropping point of purpose product.After the wax layer is warming up to predetermined temperature, increase the constant temperature stage can make wax with
Oil separation is more abundant, and time in constant temperature stage is 0.1~10.0 hour, and preferably 1.0~8.0 hours, most preferably 2.0~
5.0 hour.
In method of the invention, the heating rate and cooling rate of said wax layer can pass through air bath, water-bath, oil bath
Or other feasible modes are controlled, it is preferred to use water-bath or oil bath.Wax layer heating is controlled using water-bath or oil bath mode
When rate and rate of temperature fall, collet can be increased outside sweating ware, collet is connected with removable coil pipe and the circulatory system, the circulatory system
With program cooling/heating function, the substances such as water or conduction oil are added as circulatory mediator in the circulatory system；Coil pipe is soaked after charging
Not and be fixed in wax layer, can make wax layer lifting/lowering temperature process faster, wax layer more uniform temperature.
In method of the invention, wax layer is forced air flow through described in step (3) can be real in sweating effort any stage
It applies, preferably implements at sweating initial stage.
In method of the invention, wax layer is forced air flow through described in step (3) and is utilized in increase air pressure above wax layer
It realizes, can such as apply the gauge of 0.2~2.0 atmospheric pressure above wax layer, and remain normal pressure below wax layer.
In method of the invention, wax layer is forced air flow through described in step (3) and is utilized in reduction air pressure below wax layer
It realizes, normal pressure can be such as kept above wax layer, and maintain the gauge of -0.2~-0.8 atmospheric pressure below wax layer.
In method of the invention, the composition of hot melt adhesive in mass described in step (B) are as follows: viscosity modifier 75.0%~
85.0%, basic resin 10.0%~15.0%, tackifying resin 4.9%~9.0%, antioxidant 0.1%~1.0%.
In method of the invention, basic resin described in step (B) can be one in EVA, SBS, SIS, SEBS, PIB
Or mixtures thereof kind；The tackifying resin can be C5 resin, C9 resin, hydrogenated aromatic Petropols, terpene resin, pine
Or mixtures thereof one of botany bar gum, rosin glycerides, hydrogenated rosin, hydrogenated rosin glyceride；The antioxidant can be with
It is antioxidant BHT, antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 1330, antioxidant 3114, antioxidant 164, resists
Or mixtures thereof one of oxygen agent 168, antioxidant 264, antioxidant B215, antioxidant B225.
In method of the invention, the allocation process of hot melt adhesive described in step (B) are as follows: weigh viscosity tune in the ratio of determination
Save the materials such as agent, basic resin, tackifying resin, antioxidant；Viscosity modifier is divided into three parts: by a viscosity modifier
Antioxidant is added after heating fusing, basic resin is added after being warming up to 160 DEG C~180 DEG C, stirs to uniformly mixed；It is added second
Part viscosity modifier and tackifying resin are stirred to uniformly mixed；It is eventually adding third part viscosity modifier and is uniformly mixed, it is cooling
It is afterwards hot melt adhesive product.
Sweating de-oiling method is to be separated using wax and oil property with different melting points to produce pertroleum wax, for petroleum
Wax sweating process studies have shown that liquid composition is gradually discharged along crystalline portion in sweating effort, be similar to liquid and exist
The case where being flowed in capillary.For commercially available crystallite wax product, since its main component is isoparaffin and cycloalkane, chemical group
At complexity, cause crystals upon crystallization structure more fine and compact, huge filter flow resistance power is formed to the discharge of liquid composition, this is just
Wax and oil in the common sweating effort for only leaning on gravity natural separation is caused to be difficult to be kept completely separate.Therefore common sweating process cannot have
Effect reduces the oil content of microwax.
The present invention is in order to allow this solvent-free de-oiling method of sweating to produce the hot melt adhesive viscosity-adjusting agent of low oil content
Agent is difficult to the reason of separating for solids fraction and liquid composition, forces air flow through wax layer by using in sweating effort
The method for carrying out liquid composition forces solids fraction and liquid composition separation, enhances separating effect and accelerates separation speed
Degree；Increasing the high temperature constant temperature stage in crystallization process can make the crystallization of wax bigger, be conducive to liquid composition in sweating effort
Discharge.For microwax crystallization process studies have shown that the chemical composition of microwax be determine crystal habit main factor,
The condition of cooling procedure also will affect crystal habit simultaneously, especially near dropping point at a temperature of cooling condition to crystallization
The influence of form is most obvious.Microwax has partially crystallizable when being cooled near dropping point and is precipitated, this partially crystallizable body can be with
As the nucleus for being subsequently formed crystallization, increase the high temperature constant temperature stage at this time, nucleus can be enable sufficiently to increase, forms bigger ruler
Very little crystal, although this larger sized crystal is coarse not as good as the crystallization of soap manufacturing paraffin and low melt point paraffin, to sweating
It is also highly beneficial that liquid composition, which is discharged, in stage.Simultaneously further preferably by sweating raw material in bubble stabilizer and mechanical agitation
Under be passed through gas, these gases can form stable, evenly dispersed small gas under the action of bubble stabilizer in wax layer
Bubble.Studies have shown that bubble stabilizer of the HLB value between 4~10 is selected to can produce relatively stable bubble, and HLB value 6~
Bubble stabilizer between 8 can produce fine and smooth foaming structure and stability is more preferable；And use anionic surfactant with
When cationic surface active agent compounds, due to the strong electrostatic interaction of the two, suction of the anions and canons on gas-liquid interface is increased
Attached amount, and increase liquid phase viscosity between film, so that the stability of bubble greatly improved, in other words in the case where less dosage
Stable bubble can be formed.In sweating effort, these uniform, tiny bubbles are easy to be formed in wax layer several tiny
Channel is conducive to the discharge of liquid composition, research shows that the volume fraction of bubble solids fraction and liquid composition when within 10%
The trend of separating effect enhancing is more apparent, and the increase of bubble volume fraction slows down to the effect tendency of separating effect thereafter；It is selected
Surfactant fusing point or freezing point are lower than the maximum temperature of sweating effort, and contain functional group, with the intermiscibility of paraffin compared with
Difference can be discharged in sweating effort with liquid composition.Being aided with the cryogenic thermostat stage again keeps solid crystal more abundant, Yi Jifa
It is the methods of more abundant that the constant temperature stage of sweat process separates solids fraction and liquid composition, significantly reduces the oil-containing of product
Amount, allows sweating process to produce hot melt adhesive viscosity modifier.
By viscosity modifier and basic resin, tackifying resin and antioxidant, melting mixing is uniformly hot melt adhesive in proportion
Product can be used for aluminum foil seal gasket.
This have the advantage that: the method for carrying out liquid composition by wax layer using air-flow in sweating effort is strong
The separation of solids fraction processed and liquid composition enhances separating effect and accelerates separating rate；Increased using high temperature crystallization brilliant
Body size, while micro-bubble is formed in wax layer using gas, it is also beneficial to the quick discharge of liquid composition；And increase low temperature
The processes such as constant temperature stage and the constant temperature stage of sweating effort, so that sweating process be allow to prepare the crystallite of low oil content
Wax can be used as the viscosity modifier of hot melt adhesive；Viscosity modifier is melted with basic resin, tackifying resin and antioxidant in proportion again
Being uniformly mixed is hot melt adhesive product.The method of the present invention is low with investment of production equipment, production process is simple and operating cost is low,
Safety, energy conservation and solvent-free pollution and dust emission, hot melt adhesive product have many advantages, such as that curing time is short, heat-resist.
Specific embodiment
The present invention is raw material by selecting suitable microwax, and on the basis of common sweating process, sweating ware top connects
It connects dismountable sealing device and is connect with pressurized buffer tank and compressor, and/or connect pressure-reducing cushioning tank in sweating ware lower part
And vacuum pump；The heating of sweating raw material melts and is preferably added to bubble stabilizer, is packed into sweating ware after forming stable micro-bubble；
Wax layer heating-cooling speed is controlled with water-bath；Wax layer temperature be down to raw material dropping point temperature nearby and high temperature constant temperature for a period of time；After
It is continuous to be cooled to preset temperature and cryogenic thermostat for a period of time；In sweating effort, start compressor with formed above just in wax layer
Pressure, and/or starting vacuum pump is in wax layer negative pressure formed below, to force air flow through wax layer；Wax layer temperature reaches default
Simultaneously constant temperature stops sweating effort to temperature afterwards for a period of time；It is pressed again with basic resin, tackifying resin and antioxidant after refining on wax
Ratio melting mixing is uniformly hot melt adhesive product.
The method that 1-2 illustrates present invention preparation hot melt adhesive by the following examples.It is involved below if nothing especially indicates
And % is mass percent, the pressure is gauge pressure.
Embodiment 1
The present embodiment includes: that (A) sweating and (B) deploy two parts.
(A) it sweating: is risen including (1) preparation, (2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization, (3)
Temperature-constant temperature sweating, (4) refine four steps.
(1) preparation
The sealing system of sweating ware and pressurized buffer tank and compressor are connected；Pressure-reducing cushioning is installed in sweating ware lower part
Tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, coil pipe is fixed on sweating ware；With
Water is heat medium；The heating function for starting the circulatory system, makes recirculated water be warming up to 92 DEG C.Water is padded below sweating ware ware plate.
No. 85 microwaxes (Sinopec Henan Oil Field branch company, 82.4 DEG C of dropping points, oil content 2.08%, kinematic viscosity
(100 DEG C) 15.39mm2/ s) it is heated to addition 0.5% diethylene glycol monolaurate, 0.1% benzene sulfonamide after 92 DEG C of fusings
Sour sodium and 0.1% triacetamide oleate, be passed through air after mixing, while with colloid mill under the rate of 2500r/min
Stirring to sweating raw material volume increases by 6%, stops being passed through after air again with the rate stirring 10min of 7500r/min to be formed
Sweating ware is added after even, tiny bubble.The sealing system of sweating ware is installed.
(2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization
Start the refrigerating function of the circulatory system, controlling wax layer temperature declines wax layer temperature with the rate of temperature fall of 1.5 DEG C/h
To 84.5 DEG C and 2.5 hours progress high temperature constant temperatures of constant temperature, so that crystal sufficiently increases；Wax is made with the rate of temperature fall of 1.0 DEG C/h again
Layer temperature drops to 72.0 DEG C so that wax layer crystallizes to form solid, and constant temperature 3.0h is so that wax layer crystallization is more abundant.Close circulation
The refrigerating function of system.
(3) heating-constant temperature sweating
Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (I) is to receive under wax；Start compressor and keeps adding
Pressure buffering pressure inside the tank is stablized keeps normal pressure below 1.5~1.7 atmospheric pressure, sweating ware ware plate；Start circulation system
Function makes wax layer temperature be increased to 80.0 DEG C with the heating rate of 1.5 DEG C/h.Stop compressor.
It opens vacuum pump and pressure-reducing cushioning pressure inside the tank is kept to stablize the air pressure above -0.4~-0.6 atmospheric pressure, wax layer
Keep normal pressure；Wax layer temperature is set to be increased to 82.5 DEG C and constant temperature 4.0 hours with the heating rate of 1.0 DEG C/h, so that in wax layer
Solids fraction and liquid composition are sufficiently separated.Stop vacuum pump, terminates sweating effort.
Sweating ware exports changing-over crude product storage tank (I) to receive on wax；Continue the temperature of raising recirculated water to 95 DEG C, with molten
Change and take out on wax, as crude product (I).
(4) it refines
Crude product (I) is hot melt adhesive after clay-filtered with viscosity modifier (I), stand-by after molding.
Hot melt adhesive viscosity modifier (I) property: dropping point: 84.3 DEG C, oil content: 0.78%, kinematic viscosity (100 DEG C)
15.20mm2/ s meets the index request of aluminum foil seal gasket hot melt adhesive viscosity modifier.
The yield of hot melt adhesive viscosity modifier (I) is 30.2%(relative to raw material microwax).
(B) it deploys
It weighs viscosity modifier (I) 8.0Kg and is divided into three parts.It will be added after the heating fusing of a viscosity modifier
The bright Sheng of BHT() 0.05Kg, tri- well of EVA-28/150(is added after being warming up to 160 DEG C~180 DEG C) in 0.4Kg and SEBS YH-502(
Petrochemical industry Ba Ling company, state) 0.8Kg, is stirred to uniformly mixed；Second portion of viscosity modifier and C5 hydrogenated petroleum resin (No. 0) is added
(Zhejiang Henghe material Science and Technology Co., Ltd.) 0.75Kg is stirred to uniformly mixed；It is eventually adding third part viscosity modifier
And be uniformly mixed, it is hot melt adhesive product (I) after cooling.
Hot melt adhesive product (I) property: shear strength: 46N/cm, softening point: 81 DEG C, curing time: 3s, resist 50 DEG C of high temperature:
15h。
Said ratios and production technology are repeated with No. 85 microwaxes (with embodiment 1) substitution viscosity modifier (I), are obtained pair
Than hot melt adhesive product (I).Compare hot melt adhesive product (I) property: 44 N/cm of shear strength, softening point: 67 DEG C, curing time:
8s, resist 50 DEG C of high temperature: 3h.
From hot melt adhesive product (I) and comparison hot melt adhesive product (I) property it can be seen that the two shear strength is about the same,
And hot melt adhesive product (I) softening point is higher by 14 DEG C, curing time and anti-50 DEG C of high-temperature times significantly improve.
Embodiment 2
The present embodiment includes: that (A) sweating and (B) deploy two parts.
(A) it sweating: is risen including (1) preparation, (2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization, (3)
Temperature-constant temperature sweating, (4) refine four steps.
(1) preparation
The sealing system of sweating ware and pressurized buffer tank and compressor are connected；Pressure-reducing cushioning is installed in sweating ware lower part
Tank simultaneously connects vacuum pump；Sweating ware collet and removable coil pipe are connect with the circulatory system, coil pipe is fixed on sweating ware；With
Water is heat medium；The heating function for starting the circulatory system, makes recirculated water be warming up to 92 DEG C.Water is padded below sweating ware ware plate.
No. 85 microwaxes (with embodiment 1) be heated to 92 DEG C fusing after be added 1.0% sorbitan monopalmitate,
0.2% N- methyl oil amide groups sodium taurocholate and 0.2% cetyl trimethylammonium bromide, are passed through titanium dioxide after mixing
Carbon, while stirred under the rate of 2000r/min with colloid mill to sweating raw material volume and increasing by 9%, after stopping is passed through carbon dioxide
Again with the rate stirring 10min of 7000r/min to form addition sweating ware after uniform, tiny bubble.The close of sweating ware is installed
Envelope system.
(2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization
Start the refrigerating function of the circulatory system, controlling wax layer temperature declines wax layer temperature with the rate of temperature fall of 2.0 DEG C/h
To 84.5 DEG C and 2.0 hours progress high temperature constant temperatures of constant temperature, so that crystal sufficiently increases；Wax is made with the rate of temperature fall of 1.5 DEG C/h again
Layer temperature drops to 72.0 DEG C so that wax layer crystallizes to form solid, and constant temperature 2.0h is so that wax layer crystallization is more abundant.Close circulation
The refrigerating function of system.
(3) heating-constant temperature sweating
Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (II) is to receive under wax；Starting compressor is simultaneously kept
Pressurized buffer pressure inside the tank is stablized keeps normal pressure below 1.5~1.7 atmospheric pressure, sweating ware ware plate；The starting circulatory system adds
Heat function makes wax layer temperature be increased to 80.0 DEG C with the heating rate of 2.0 DEG C/h.Stop compressor.
It opens vacuum pump and pressure-reducing cushioning pressure inside the tank is kept to stablize the air pressure above -0.4~-0.6 atmospheric pressure, wax layer
Keep normal pressure；Wax layer temperature is set to be increased to 82.5 DEG C and constant temperature 3.0 hours with the heating rate of 0.5 DEG C/h, so that in wax layer
Solids fraction and liquid composition are sufficiently separated.Stop vacuum pump, terminates sweating effort.
Sweating ware exports changing-over crude product storage tank (II) to receive on wax；Continue increase recirculated water temperature to 95 DEG C, with
Fusing is taken out on wax, as crude product (II).
(4) it refines
Crude product (I) is hot melt adhesive after clay-filtered with viscosity modifier (II), stand-by after molding.
Hot melt adhesive viscosity modifier (II) property: dropping point: 84.1 DEG C, oil content: 0.56%, kinematic viscosity (100
DEG C) 15.12mm2/ s meets the index request of aluminum foil seal gasket hot melt adhesive viscosity modifier.
The yield of hot melt adhesive viscosity modifier (II) is 34.6%(relative to raw material microwax).
(B) it deploys
It weighs viscosity modifier (II) 8.30Kg and is divided into three parts.It will be added after the heating fusing of a viscosity modifier
Think this big Chemical Co., Ltd. in the Jiangsu antioxidant 1330() 0.04Kg, EVA-28/250 is added after being warming up to 160 DEG C~180 DEG C
(three wells) 0.36Kg and SEBS YH-501(Sinopec Ba Ling company) 0.70Kg, is stirred to uniformly mixed；Second part is added to glue
Regulator and C9 hydrogenated petroleum resin (No. 0) (Jinan Nuo Chuan Chemical Co., Ltd.) 0.60Kg are spent, is stirred to uniformly mixed；Finally
Third part viscosity modifier is added and is uniformly mixed, is hot melt adhesive product (II) after cooling.
Hot melt adhesive product (II) property: shear strength: 47N/cm, softening point: 82 DEG C, curing time: 2s, resist 50 DEG C of height
Temperature: 16h.
Said ratio and production technology are repeated with No. 85 microwax (with embodiment 1) substitutions viscosity modifier (II), is obtained
It compares hot melt adhesive product (II).Compare hot melt adhesive product (II) property: shear strength: 44 N/cm, softening point: when 66 DEG C, solidification
Between: 9s, resist 50 DEG C of high temperature: 4h.
From hot melt adhesive product (II) and comparison hot melt adhesive product (II) property it can be seen that the two shear strength substantially phase
When, and hot melt adhesive product (II) softening point is higher by 16 DEG C, curing time and anti-50 DEG C of high-temperature times significantly improve.
The method that can be seen that preparation hot melt adhesive of the invention by embodiment 1-2, by increasing pressurization and/or vacuum
The improvement to sweatbox such as facility；By sweating raw material is mixed into after bubble stabilizer formed in wax layer using gas it is small
The improvement to sweating process such as bubble, the constant temperature stage for increasing crystallization and sweating effort；Enhance solids fraction and liquid composition
Separating effect and accelerate separating rate, so that sweating process be allow to produce the hot melt adhesive viscosity-adjusting agent of low oil content
Agent；Viscosity modifier is again aluminum foil seal gasket hot melt adhesive product with the allotment of basic resin, tackifying resin and antioxidant.From applying
Hot melt adhesive product (I), (II) and comparison hot melt adhesive product (I), (II) prepared by example 1-2 is as can be seen that the method for the present invention preparation
Hot melt adhesive product have many advantages, such as that curing time is short, heat-resist.
Claims (23)
1. a kind of method for preparing hot melt adhesive, including the following contents:
(A) sweating
(1) using the commodity microwax that dropping point is 75 DEG C~85 DEG C as sweating raw material, bubble preparation: is added after heating fusing
Stabilizer is passed through gas under stiring and is packed into sweatbox after forming stable micro-bubble；
(2) it crystallizes: wax layer is cooled to by sweating raw material dropping point~+4.0 DEG C of dropping point with 1.0 DEG C/h~3.0 DEG C/h rate
And high temperature constant temperature 0.1~6.0 hour；5 DEG C of sweating raw material dropping point or less is cooled to 0.5 DEG C/h~2.5 DEG C/h rate again
~20 DEG C of predetermined temperature simultaneously cryogenic thermostat 0.1~5.0 hour；
(3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature 0.1~10.0 hour
After stop sweating；Wax layer is forced air flow through in sweating effort；The predetermined temperature is -10 DEG C~mesh of purpose product dropping point
- 1 DEG C of product dropping point；
(4) it refines: being hot melt adhesive viscosity modifier after refining on wax；
(B) it deploys: the viscosity modifier of step (4) preparation and basic resin, tackifying resin and antioxidant being melted in proportion mixed
Closing uniformly is hot melt adhesive product；The hot melt adhesive product forms in mass are as follows: viscosity modifier 75.0%~85.0%, basic
Resin 10.0%~15.0%, tackifying resin 4.9%~9.0%, antioxidant 0.1%~1.0%.
2. according to the method for claim 1, which is characterized in that the bubble stabilizer is selected from non-ionic surfactant
One group of substance that agent, anionic surfactant, cationic surface active agent, amphoteric surfactant are constituted；Bubble
The freezing point or fusing point of stabilizer are lower than the maximum temperature of step (3) sweating.
3. according to the method for claim 2, which is characterized in that the HLB value of the bubble stabilizer is 4~10.
4. according to method described in claim 2 or 3, which is characterized in that the nonionic surface active agent is selected from dehydration
Sorbitol monooleate, sorbitan monostearate, diethylene glycol aliphatic ester, sorbitan monopalmitate, four
Ethylene glycol monostearate, polyoxypropylene stearate, sorbitan mono-laurate, polyoxyethylene fatty acid ester are constituted
One group of substance；The anionic surfactant is selected from fatty alcohol sulfate monoethanolamine salt, alkyl polyoxyethylene ether sulphur
Sour sodium, oleamide yl carboxylic acid sodium, sodium alkyl benzene sulfonate, N- methyl oleoyl taurate, sodium butylnaphthalenesulfonate, succinate sulphur
Sour sodium, the one group of substance constituted along succinate monoester sodium sulfonate；The cationic surface active agent be selected from benzyl quaternary ammonium salt,
Dodecyl benzyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl three
One group of substance that ammonio methacrylate, triacetamide oleate are constituted；The amphoteric surfactant is selected from dodecyl sweet tea
Dish alkali, dodecyldimethyl ammonium oxide, aliphatic group imidazolidine derivatives, alkyl imidazoline derivatives, derivative of fatty acid,
One group of substance that amphoteric modified epoxy ethane additive product is constituted.
5. according to the method for claim 2, which is characterized in that the bubble stabilizer is non-ionic surfactant
One group of substance that agent, anionic surfactant and cationic surface active agent mixing are constituted.
6. according to the method for claim 1, which is characterized in that the bubble stabilizer additional amount is sweating material quality
0.01%~10.0%.
7. according to the method for claim 1, which is characterized in that the gas be air, carbon dioxide, in nitrogen extremely
Few one kind.
8. according to the method for claim 1, which is characterized in that the stirring use colloid mill, revolving speed be 500~
10000 r/min。
9. according to the method for claim 1, which is characterized in that the mixed gas account for sweating raw material volume 2%~
20%。
10. according to the method for claim 1, which is characterized in that predetermined temperature described in step (2) is sweating raw material drop
8 DEG C~15 DEG C below fusing point.
11. according to the method for claim 1, which is characterized in that force air flow through wax layer use described in step (3)
Increase air pressure above wax layer and/or reduce air pressure below wax layer, so that wax layer upper and lower is formed pressure difference and realize, the pressure
Power difference is 0.1~5.0 atmospheric pressure.
12. according to the method for claim 1, which is characterized in that described forces air flow through wax layer in sweating initial stage reality
It applies.
13. according to the method for claim 11, which is characterized in that the wax layer that forces air flow through uses in wax layer
Fang Zengjia air pressure is realized, applies the gauge of 0.2~2.0 atmospheric pressure above wax layer, and remains normal pressure below wax layer.
14. according to the method for claim 11, which is characterized in that the wax layer that forces air flow through uses under wax layer
Side reduces air pressure and realizes, air pressure keeps normal pressure above wax layer, and the table of -0.2~-0.8 atmospheric pressure is maintained below wax layer
Pressure pressure.
15. according to the method for claim 1, which is characterized in that the sweatbox is sweating ware.
16. according to the method for claim 1, which is characterized in that basic resin described in process (B) be selected from EVA, SBS,
At least one of SIS, SEBS, PIB.
17. according to the method for claim 1, which is characterized in that tackifying resin described in process (B) be selected from C5 resin,
C9 resin, hydrogenated aromatic Petropols, terpene resin, rosin resin, rosin glycerides, hydrogenated rosin, hydrogenated rosin glycerol
At least one of ester.
18. according to the method for claim 1, which is characterized in that antioxidant described in process (B) be selected from antioxidant BHT,
Antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 1330, antioxidant 3114, antioxidant 164, irgasfos 168, antioxygen
At least one of agent 264, antioxidant B215, antioxidant B225.
19. according to the method for claim 1, which is characterized in that the allocation process of hot melt adhesive described in process (B) are as follows: press
The ratio of determination weighs viscosity modifier, basic resin, tackifying resin and antioxidant；Viscosity modifier is divided into three parts；
Antioxidant will be added after the heating fusing of a viscosity modifier, basic resin is added after being warming up to 160 DEG C~180 DEG C, stirring is extremely
It is uniformly mixed；Second portion of viscosity modifier and tackifying resin is added, stirs to uniformly mixed；It is eventually adding third part viscosity-adjusting agent
Agent is simultaneously uniformly mixed, and is hot melt adhesive product after cooling.
20. according to the method for claim 3, which is characterized in that the HLB value of the bubble stabilizer is 6~8.
21. according to the method for claim 6, which is characterized in that the bubble stabilizer additional amount is sweating raw material matter
The 0.1%~2.0% of amount.
22. according to the method for claim 9, which is characterized in that the mixed gas account for sweating raw material volume 5%~
10%。
23. according to the method for claim 11, which is characterized in that the pressure difference is 0.2~2.0 atmospheric pressure.
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