CN107513422B

CN107513422B - The production method of hot melt adhesive microwax

Info

Publication number: CN107513422B
Application number: CN201610432813.7A
Authority: CN
Inventors: 孙剑锋; 何凤友; 张志银; 吴颖; 袁平飞; 毕文卓
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2016-06-17
Filing date: 2016-06-17
Publication date: 2019-06-11
Anticipated expiration: 2036-06-17
Also published as: CN107513422A

Abstract

The invention discloses a kind of production methods of hot melt adhesive microwax.This method is on the basis of common sweating de-oiling technique, the oil of liquid is carried out to force separation wax and oil by wax layer using air-flow in sweating effort, preferably raw material and water or salting liquid are emulsified simultaneously, it is also beneficial to the quick discharge of oil, so that sweating de-oiling method be allow to produce the hot melt adhesive crystallite wax product of low oil content.The method of the present invention has many advantages, such as that equipment investment is low, production process is simple and operating cost is low, safety, energy conservation and solvent-free pollution.

Description

The production method of hot melt adhesive microwax

Technical field

The invention belongs to Wax special production technical fields, more particularly to a kind of production method of hot melt adhesive microwax.

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.It is the most important kind of hot melt adhesive with the EVA hot-melt adhesive that ethylene-vinyl acetate random copolymer (EVA) is basic resin.

EVA hot-melt adhesive is by basic resin, tackifying resin, viscosity modifier and antioxidant etc. at being grouped as.Basic resin is EVA resin, ratio, quality determine the basic performance (cementitiousness, melting temperature and the adhesion strength of such as glue) of hot melt adhesive. The mobility of colloid and the wetability to adherend can be improved in tackifying resin, improves adhesive property, and the bonding for reaching required is strong Degree.The effect of viscosity modifier is the mobility for increasing colloid molten state, adjusts setting rate, is quickly firmly bonded with reaching Purpose.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.In addition, also one can be mixed according to the difference of temperature, area The cold-resistance agent of a little suitable frigid zone temperature or the antiheat agent for being suitble to tropical temperature, can also be added a small amount of filler to increase interstitial and drop Low cost.

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 aluminum foil seal gasket hot melt adhesive, it is desirable that use dropping point 80~88 DEG C, oil content be not more than 1.0%(mass content), (100 DEG C) of kinematic viscosity be not less than 10 mm²The microwax conduct of/s Viscosity modifier.

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.

Common sweating de-oiling technique 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) crystallize: by raw material with Rate of temperature fall no more than 4 DEG C/h progressively cools to 10~20 DEG C of its fusing point or less.In cooling procedure, various components press fusing point Sequence from high to low successively crystallizes and forms solid；(3) sweating: after wax layer temperature reaches preset cooling final temperature, Bleed off pad water；Raw material is slowly heated to preset sweating final temperature again.In sweating effort, various components by fusing point by Low to high sequence be successively fused into liquid and flow out the wax layer residue (on wax) finally obtained (under wax) be exactly high-melting-point, The wax of low oil-containing；(4) it refines: collecting crude product and (continue to increase temperature after sweating effort, be taken out on wax with fusing, as Crude 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 Filter afterwards) 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 the oil content using the method for extending sweating sessions and improving sweating final temperature, on sweating later period wax Unrelated with yield, i.e., the oil content on wax does not decline with the decline of yield, so common sweating de-oiling technique cannot produce drop Hot melt adhesive crystallite wax product of the fusing 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, the demand using sweating de-oiling technique production hot melt adhesive microwax is more compeled It cuts.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of production method of hot melt adhesive microwax.Specifically Using sweatbox, on the basis of common sweating process, carried out after emulsion preferably is made with water or salting liquid in paraffin Sweating is conducive to the discharge of fluid oil；The oil of liquid is carried out to force by wax layer using air-flow in sweating effort simultaneously Wax and oil are separated, separating effect is enhanced and accelerates separating rate, produce this solvent-free de-oiling method of sweating Hot melt adhesive crystallite wax product.The method of the present invention is low with equipment investment, production process is simple and operating cost is low, energy-saving safe And the advantages that solvent-free pollution.

A kind of production method of hot melt adhesive microwax of the invention, including the following contents:

A: emulsification

(A1) prepared by oil phase material: the commodity microwax for being 75 DEG C~85 DEG C using dropping point is raw material, heating fusing；It is added Oil soluble emulsifying agent stirs evenly, and forms oil phase material；

(A2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；

(A3) prepared by emulsion: water-phase material being added in oil phase material under agitation, is continued after all adding Stirring 5~60 minutes；

B: sweating

(B1) emulsion of (A3) process preparation preparation: is packed into sweatbox；

(B2) it crystallizes: emulsion being first cooled to by+4 DEG C of raw material dropping point~drop with 1.0 DEG C/h~25.0 DEG C/h rate + 10 DEG C of fusing point, then wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h rate, high temperature constant temperature is for a period of time；Again 5 DEG C~20 DEG C of raw material dropping point or less of cooling final temperature is cooled to 0.5 DEG C/h~2.5 DEG C/h rate, and low temperature is permanent Warm a period of time；

(B3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature for a period of time After stop sweating；Wax layer is forced air flow through in sweating effort；

(B4) it refines: being hot melt adhesive crystallite wax product after refining on wax.

In method of the invention, the dropping point of the source commodity microwax is 75 DEG C~85 DEG C, and oil content is generally 1.0%~5.0%(mass content).

In method of the invention, the oil soluble emulsifying agent is selected from nonionic surface active agent, anionic surface In one group of substance that activating agent, cationic surface active agent, amphoteric surfactant, response type surfactant active are constituted It is one or more of.The HLB value of oil soluble emulsifying agent is 1~10, preferably 3~8；The fusing point or freezing point of the surfactant Maximum temperature (i.e. predetermined temperature described in step B3) is heated up lower than sweating.The oil soluble emulsifying agent be preferably two kinds with The compound emulsifying agent that upper surface activating agent is constituted.

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.

The response type surfactant active can be reacted with ammonia water by organic acid, and Organic Alcohol is added and is made.Specifically: Organic acid and ammonium hydroxide are stirred to react 5 under conditions of 10~30 DEG C~generate organic acid ammonium salt after sixty minutes；In 60~70 DEG C of item Under part, Organic Alcohol is added into the organic acid ammonium salt prepared, stirring is uniformly mixed it.

The organic acid is saturation and unsaturated acids of the carbon number 1~36, and preferably carbon number is organic in 8~20 unitary Acid can be caprylic acid, acid of the positive tenth of the twelve Earthly Branches, n-capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitinic acid, hard One or more mixtures of resin acid, linoleic acid, oleic acid, nonadecanoic acid, arachidic acid；Be also possible to polyacid, as oxalic acid, At least one of malic acid, citric acid, maleic acid, fumaric acid.

The mass concentration of the ammonium hydroxide is 1%~28%, preferably 5%~15%.The Organic Alcohol be carbon number 1~12 it is full And monohydric alcohol, preferably or mixtures thereof one of methanol, ethyl alcohol.The mixing speed is 50~1500r/min, preferably 100~1000r/min.It uses in the sweating effort of reactive emulsifier with the mass ratio of the acid such as sulfuric acid, nitric acid as 2%~20% Aqueous solution absorb ammonia.

In method of the invention, the salting liquid be any water-soluble salt solution, preferably chemical property it is stable, it is nontoxic, It is non-corrosive, without special odor, salting liquid cheap and easy to get.Salting liquid can be sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, The aqueous solution of or mixtures thereof one of sodium sulphate, potassium sulfate.Concentration of salt solution is 1%~30%(mass, similarly hereinafter), preferably 5% ~20%.

The proportion of the emulsion are as follows: paraffin 60.0%~90.0%, preferably 65.0%~84.0%；Water or salting liquid； 9.9%~30.0%, preferably 15.0%~30.0%；Compound emulsifying agent 0.1%~10.0%, preferably 1.0%~5.0%.The emulsification Condition are as follows: at 85 DEG C~98 DEG C, mix 5~60 minutes with 50~1500 revs/min of mixing speed, preferably 85 DEG C~ At 95 DEG C, mixed 10~30 minutes with 100~1000 revs/min of mixing speed.

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.In the sweating effort of step (B3), the wax layer that forces air flow through is used in wax Layer top increases air pressure and/or reduces air pressure below wax layer, so that wax layer upper and lower is formed pressure difference and realizes.The pressure Difference is generally 0.1~5.0 atmospheric pressure, preferably 0.2~2.0 atmospheric pressure, to force air flow through wax layer.

In method of the invention, in the temperature-fall period of step (B2) described crystallization, preferred raw material wax layer first with 2.0 DEG C/h~ The rate of 20.0 DEG C/h is cooled within the scope of+4 DEG C of raw material dropping point~+8 DEG C of dropping point；Thereafter the drop before high-temperature constant temperature section Warm rate preferably 1.5 DEG C/h~2.5 DEG C/h.The proper temperature of the high-temperature constant temperature section of the temperature-fall period is paraffin drip melt - 1.0 DEG C of point~+4.0 DEG C of dropping point, preferably paraffin dropping point~+2.0 DEG C of dropping point.The high-temperature constant temperature section of cooling procedure Time be 0.1~4.0 hour, preferably 0.5~4.0 hour, more preferably 1.0~4.0 hours.

In method of the invention, rate of temperature fall of the temperature-fall period of step (B2) described crystallization after high-temperature constant temperature section is excellent Select 1.0 DEG C/h~2.0 DEG C/h.The cooling final temperature is preferably 8 DEG C~15 DEG C of paraffin dropping point or less.The drop After temperature to final temperature, increasing the cryogenic thermostat stage so that solid crystal is more abundant, the time in cryogenic thermostat stage is 0.1~ 3.0 hours, preferably 0.5~3.0 hour, more preferably 1.0~3.0 hours.

In method of the invention, the heating rate preferably 1.0 DEG C/h~2.0 DEG C/h of step (B3) described sweating effort.Institute The predetermined temperature (i.e. final temperature) for stating heating is lower than 1 DEG C~10 DEG C of dropping point of purpose product.Described being warming up to is predetermined After temperature, the increase constant temperature stage can be such that wax separates with oil more sufficiently, and the time in constant temperature stage is 0.1~5.0 hour, preferably 0.5~5.0 hour, most preferably 1.0~5.0 hours.

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, collet, disk Pipe etc. can make wax layer lifting/lowering temperature process faster, wax layer more uniform temperature；The circulatory system has program cooling/heating function, circulation The substances such as water or conduction oil are added as circulatory mediator in system.

In method of the invention, wax layer is forced air flow through described in step (B3) can be in sweating effort any stage Implement, preferably implements at sweating initial stage.

In method of the invention, wax layer is forced air flow through described in step (B3) and is utilized in increase gas above wax layer What pressure was realized, it can such as apply the pressure of 0.2~2.0 atmospheric pressure (gauge pressure) above wax layer, and normal pressure is remained below wax layer.

In method of the invention, wax layer is forced air flow through described in step (B3) and is utilized in reduction gas below wax layer What pressure was realized, normal pressure can be such as kept above wax layer, and the pressure of -0.2~-0.8 atmospheric pressure (gauge pressure) is maintained below wax layer Power.

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 oil is gradually discharged along crystalline portion in sweating effort, be similar to liquid in capillary The case where middle flowing.For commercially available crystallite wax product, since its main component is isoparaffin and cycloalkane, chemical composition is multiple It is miscellaneous, cause crystals upon crystallization structure more fine and compact, huge filter flow resistance power is formed to the discharge of oil, this is resulted in only by weight Wax and oil are difficult to be kept completely separate in the common sweating effort of power natural separation.Therefore crystallite cannot be effectively reduced in common sweating process The oil content of wax.

The present invention is in order to allow this solvent-free de-oiling method of sweating to produce hot melt adhesive crystallite wax product, by general The further investigation of logical sweating effort, is difficult to the reason of separating with oil for wax, by logical using pressure air-flow in sweating effort It crosses wax layer and carries fuel-displaced method and oil is forced to separate with wax, enhance separating effect and accelerate separating rate；In crystallization process The middle increase high temperature constant temperature stage can make the crystallization of wax bigger, be conducive to discharge oily in sweating effort.For crystallite wax crystallization Process studies have shown that the chemical composition of microwax is to determine the main factor of crystal habit, while the condition of cooling procedure Also will affect crystal habit, especially near dropping point at a temperature of influence of the cooling condition to crystal habit it is most obvious. Microwax has partially crystallizable when being cooled near dropping point and is precipitated, this partially crystallizable body, which can be used as, is subsequently formed crystallization Nucleus increases the high temperature constant temperature stage at this time, nucleus can be enable sufficiently to increase, and forms larger sized crystal, this bigger It is also very to sweating stage discharge oil although the crystal of size is coarse not as good as the crystallization of soap manufacturing paraffin and low melt point paraffin It is advantageous.Raw material and water or salting liquid are further preferably formed into w/o type emulsification under the compound emulsifying agent effect of appropriate HLB value simultaneously Liquid is evenly distributed on water or salting liquid in the form of fine particle in sweating raw material；Pass through wax using air-flow in sweating effort On the one hand layer can carry water outlet or salting liquid to form short space in wax layer, these short spaces are easy in sweating effort In forming several tiny channels in wax layer, be conducive to discharge oily in sweating effort；Another aspect air-flow can carry out liquid The oil of state is to force separation wax and oil, to enhance separating effect and accelerate separating rate.Select salting liquid as water phase, The difference in specific gravity of water phase with oily phase is increased, the velocity of discharge of the water phase in sweating effort can be accelerated, to form the logical of oil extraction as early as possible Road.Selected surfactant fusing point or freezing point are lower than the maximum temperature of sweating effort, and contain functional group, the phase with paraffin Dissolubility is poor, can be discharged in sweating effort with fluid oil.The cryogenic thermostat stage for being aided with crystallization process again makes solid knot It is the methods of more abundant that brilliant more abundant and sweating effort the constant temperature stage separates wax with oil, significantly reduces containing for product Oil mass allows sweating process to produce hot melt adhesive crystallite wax product.

This have the advantage that: enhanced by using air-flow to carry fuel-displaced method by wax layer in sweating effort The separating effect of wax and oil simultaneously accelerates separating rate；Crystalline size is increased using high temperature crystallization, while molten using water or salt Liquid forms evenly dispersed short space in wax layer, is also beneficial to the quick discharge of oil；And the low temperature for increasing crystallization process is permanent The processes such as the constant temperature stage of thermophase and sweating effort are produced so that sweating de-oiling technique be allow to produce hot melt adhesive with microwax Product, and have many advantages, such as that plant investment is low, production process is simple and operating cost is low, safety, energy conservation and solvent-free pollution environment.

Specific embodiment

Sweating ware top connects dismountable sealing device and connect with pressurized buffer tank and compressor, and/or in sweating Ware lower part connects pressure-reducing cushioning tank and vacuum pump；Sweating ware is packed into after raw material microwax and the emulsification of water or salting liquid；With water-bath control Wax layer heating-cooling speed processed；Wax layer temperature be down to raw material dropping point temperature nearby and high temperature constant temperature for a period of time；Continue to be cooled to Preset temperature and cryogenic thermostat are for a period of time；In sweating effort, start compressor in wax layer positive pressure formed above, and/or Start vacuum pump in wax layer negative pressure formed below, to force air flow through wax layer；Wax layer temperature reaches preset temperature and perseverance Stop sweating effort after warm a period of time；It is hot melt adhesive crystallite wax product after refining on wax.

1-4 illustrates the production method of hot melt adhesive microwax of the invention by the following examples.As nothing is especially said Bright, related % is mass percent below.

Embodiment 1

The present embodiment includes: A: emulsification and B: sweating two parts.

A: emulsification

This part includes the preparation of (A1) oil phase material, the preparation of (A2) water-phase material, (A3) emulsion three steps of preparation.

(A1) prepared by oil phase material

Take No. 85 microwaxes (Sinopec Henan Oil Field branch company, 82.4 DEG C of dropping point, oil content 2.08%, kinematic viscosity (100 DEG C) 15.26mm²/ s) 80.0Kg, sorbitan monooleate 1.0Kg, polyoxyethylene is added after being heated to 90 DEG C of fusings Aliphatic ester 0.5Kg, diethylene glycol monolaurate 0.5Kg, stir evenly.

(A2) prepared by water-phase material

The water of 18.0Kg is heated to 95 DEG C.

(A3) prepared by emulsion

With the oil phase material prepared in the speed stirring (A1) of 500r/min, and (A2) middle water-phase material prepared is slow It is added in oil phase material, continues to stir 30min, form water-in-oil type emulsion.

B: sweating

This part includes (B1) preparation, (B2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization, (B3) liter Temperature-constant temperature sweating, (B4) refine four steps.

(B1) 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 87 DEG C.Water is padded below sweating ware ware plate.It will (A3) sweating ware is added in the emulsion prepared in.

(B2) cooling-high temperature constant temperature-cooling-cryogenic thermostat crystallization

Emulsion stands the refrigerating function of the starting circulatory system after 1.0h, makes wax layer temperature with the rate of temperature fall of 2.0 DEG C/h 83.2 DEG C and 2.0 hours progress high temperature constant temperatures of constant temperature are dropped to, so that crystal sufficiently increases；Again with the rate of temperature fall of 1.5 DEG C/h Wax layer temperature is set to drop to 72.0 DEG C and 1.0 hours progress cryogenic thermostats of constant temperature, so that crystallization is more abundant.Close the circulatory system Refrigerating function.

(B3) heating-constant temperature sweating

Sweating ware is discharged and pads water.Sweating ware outlet connection intermediate storage tank (I) is to receive under wax；The close of sweating ware top is installed Envelope system；Starting compressor simultaneously keeps pressurized buffer pressure inside the tank to stablize in 1.1~1.3 atmospheric pressure (gauge pressure), sweating ware ware Normal pressure is kept below plate；Start circulation system function, so that wax layer temperature is increased to 77.0 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 on -0.5~-0.7 atmospheric pressure (gauge pressure), wax layer Square air pressure keeps normal pressure；Wax layer temperature is set to be increased to 82.0 DEG C and constant temperature 4.0 hours with the heating rate of 1.0 DEG C/h, so that wax Wax in layer is sufficiently separated with oil.Stop vacuum pump, terminates sweating degreasing process.

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).

(B4) it refines

Crude product (I) is hot melt adhesive after clay-filtered, molding with crystallite wax product (I).

Hot melt adhesive crystallite wax product (I) property: dropping point: 84.9 DEG C, oil content: 0.78%, kinematic viscosity (100 DEG C) 14.37mm²/ s meets the index request of aluminum foil seal gasket hot melt adhesive microwax.The hot melt adhesive receipts of crystallite wax product (I) Rate is 37.5%(relative to raw material microwax).

Embodiment 2

The present embodiment includes: A: emulsification and B: sweating two parts.

A: emulsification

(A1) prepared by oil phase material

No. 85 microwax (with embodiment 1) 80.0Kg are taken, diethylene glycol aliphatic ester is added after being heated to 90 DEG C of fusings 1.5Kg, polyoxypropylene stearate 1.0Kg, 0.5 Kg of Emulphor FM, stir evenly.

(A2) prepared by water-phase material

By the NaNO of 2.0Kg₃It is dissolved in the water of 15.0 Kg, and is heated to 95 DEG C.

(A3) prepared by emulsion

With the oil phase material prepared in the speed stirring (A1) of 500 r/min, and (A2) middle water-phase material prepared is slow Slowly it is added in oil phase material, continues to stir 30min, form water-in-oil type emulsion.

B: sweating

With embodiment 1.

Hot melt adhesive manufactured in the present embodiment crystallite wax product (II) property: dropping point: 84.6 DEG C, oil content: 0.72%, Kinematic viscosity (100 DEG C) 14.16mm²/ s meets the index request of aluminum foil seal gasket hot melt adhesive microwax.Hot melt adhesive is with micro- The yield of brilliant wax product (II) is 39.2%(relative to raw material microwax).

Embodiment 3

The present embodiment includes: A: emulsification and B: sweating two parts.

A: emulsification

(A1) prepared by oil phase material

No. 85 microwax (with embodiment 1) 80.0Kg are taken, anhydrous sorbitol list palmitinic acid is added after being heated to 90 DEG C of fusings Ester 2.5Kg, empgen BB 0.5Kg, 0.5 Kg of derivative of fatty acid, stir evenly.

(A2) prepared by water-phase material

The NaCl of 2.0Kg is dissolved in the water of 14.5 Kg, and is heated to 95 DEG C.

(A3) prepared by emulsion

B: sweating

With embodiment 1.

Hot melt adhesive manufactured in the present embodiment crystallite wax product (III) property: dropping point: 84.5 DEG C, oil content: 0.74%, Kinematic viscosity (100 DEG C) 14.67mm²/ s meets the index request of aluminum foil seal gasket hot melt adhesive microwax.Hot melt adhesive is with micro- The yield of brilliant wax product (III) is 39.6%(relative to raw material microwax).

Embodiment 4

The present embodiment includes: A: emulsification and B: sweating two parts.

A: emulsification

(A1) prepared by oil phase material

No. 85 microwax (with embodiment 1) 80.0Kg are taken, anhydrous sorbitol list palmitinic acid is added after being heated to 90 DEG C of fusings Ester 1.0Kg, diethylene glycol aliphatic ester 0.5Kg, 0.5 Kg of fatty alcohol sulfate monoethanolamine, stir evenly.

(A2) prepared by water-phase material

By the K of 2.0Kg₂SO₄It is dissolved in the water of 16.0 Kg, and is heated to 95 DEG C.

(A3) prepared by emulsion

B: sweating

With embodiment 1.

Hot melt adhesive manufactured in the present embodiment crystallite wax product (IV) property: dropping point: 84.2 DEG C, oil content: 0.79%, Kinematic viscosity (100 DEG C) 13.95mm²/ s meets the index request of aluminum foil seal gasket hot melt adhesive microwax.Hot melt adhesive is with micro- The yield of brilliant wax product (IV) is 38.8%(relative to raw material microwax).

Embodiment 5

The present embodiment includes: A: the preparation of emulsifier, B: emulsification and C sweating three parts.

A: the preparation of emulsifier

The stearic acid for weighing 3Kg is warming up to 80 DEG C of fusings and is placed in reaction kettle, and the oleic acid of 2Kg and 10% ammonium hydroxide is added 2.5Kg, starting stirring, mixing speed 500r/min cool the temperature to 60 DEG C after reacting 60min, the ethyl alcohol of 0.75Kg are added, It is stand-by after mixing to continue stirring 30min.

B: emulsification

This part includes the preparation of (B1) oil phase material, the preparation of (B2) water-phase material, (B3) emulsion three steps of preparation.

(B1) prepared by oil phase material

No. 85 microwax (with embodiment 1) 80.0Kg are taken, emulsifier prepared by A process is added after being heated to 90 DEG C of fusings 3.0Kg is stirred evenly.

(B2) prepared by water-phase material

The KCl of 2.0Kg is dissolved in the water of 15.0 Kg, and is heated to 95 DEG C.

(B3) prepared by emulsion

With embodiment 1.

C: sweating

With 5%H in sweating effort₂SO₄Solution absorbs ammonia, remaining is the same as embodiment 1.

Hot melt adhesive manufactured in the present embodiment crystallite wax product (IV) property: dropping point: 84.4 DEG C, oil content: 0.77%, Kinematic viscosity (100 DEG C) 13.82mm²/ s meets the index request of aluminum foil seal gasket hot melt adhesive microwax.Hot melt adhesive is with micro- The yield of brilliant wax product (IV) is 39.1%(relative to raw material microwax).

The production method that can be seen that hot melt adhesive microwax of the invention by embodiment 1-5 is pressurizeed by increasing And/or the improvement to sweatbox such as vacuum facility；It is formed in wax layer using the water or salting liquid of emulsification evenly dispersed micro- Small space, constant temperature stage that wax layer, increase crystallization and sweating effort are forced air flow through in sweating effort etc. are to sweating process Improvement；It enhances the separating effect of wax and oil and accelerates separating rate, so that sweating de-oiling technique be allow to produce hot melt Glue crystallite wax product.

Claims

1. a kind of production method of hot melt adhesive microwax, including the following contents:

A: emulsification

(A1) prepared by oil phase material: the commodity microwax for being 75 DEG C~85 DEG C using dropping point is raw material, heating fusing；It is molten that oil is added Property emulsifier, stir evenly, formed oil phase material；

(A2) prepared by water-phase material: water or salting liquid being heated, water-phase material is formed；The salting liquid be selected from sodium chloride solution, In one group of substance that Klorvess Liquid, sodium carbonate liquor, solution of potassium carbonate, metabisulfite solution and potassium sulfate solution are constituted at least It is a kind of；

(A3) prepared by emulsion: water-phase material being added in oil phase material under agitation, continues stirring 5 after all adding ~60 minutes；

B: sweating

(B2) crystallize: first with 1.0 DEG C/h~25.0 DEG C/h rate by emulsion be cooled to+4 DEG C of raw material dropping point~dropping point+ 10 DEG C, then wax layer is cooled to by proper temperature with 1.0 DEG C/h~3.0 DEG C/h rate, constant temperature 0.1~4.0 hour；Again with 0.5 DEG C/h~2.5 DEG C/h rate is cooled to 5 DEG C~20 DEG C of raw material dropping point or less of cooling final temperature, and constant temperature 0.1~3.0 Hour；The proper temperature is -1.0 DEG C of paraffin dropping point~+4.0 DEG C of dropping point；

(B3) sweating: with the heating of 0.5 DEG C/h~2.5 DEG C/h rate；Wax layer reaches predetermined temperature and constant temperature 0.1~5.0 hour After stop sweating；Wax layer is forced air flow through in sweating effort；

(B4) it refines: being hot melt adhesive crystallite wax product after refining on wax；

Wherein, predetermined temperature described in step (B3) is lower than 1 DEG C~10 DEG C of purpose product dropping point.

2. according to the method for claim 1, which is characterized in that the oil soluble emulsifying agent is living selected from non-ionic surface Property agent, anionic surfactant, cationic surface active agent, amphoteric surfactant, response type surfactant active The one group of substance constituted；The HLB value of oil soluble emulsifying agent is 1~10, and the fusing point or freezing point of the oil soluble emulsifying agent are lower than Sweating heating maximum temperature.

3. according to the method for claim 2, which is characterized in that the nonionic surface active agent is selected from Sorbitan Alcohol monoleate, sorbitan monostearate, diethylene glycol aliphatic ester, sorbitan monopalmitate, tetrem two Alcohol monostearate, polyoxypropylene stearate, sorbitan mono-laurate, polyoxyethylene fatty acid ester constitute one group Substance；The anionic surfactant be 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, The one group of substance constituted along succinate monoester sodium sulfonate；The cationic surface active agent is selected from benzyl quaternary ammonium salt, 12 Zephiran, dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethyl One group of substance that ammonium chloride, triacetamide oleate are constituted；The amphoteric surfactant be selected from empgen BB, Dodecyldimethyl ammonium oxide, aliphatic group imidazolidine derivatives, alkyl imidazoline derivatives, derivative of fatty acid, both sexes One group of substance that type modified epoxy ethane additive product is constituted.

4. according to the method for claim 2, which is characterized in that the oil soluble emulsifying agent is two or more surface-actives The compound emulsifying agent that agent is constituted.

5. according to the method for claim 1, which is characterized in that the mass concentration of the salting liquid is 1%~30%.

6. according to the method for claim 1, which is characterized in that mixing speed described in step (A3) is 50~1500 Rev/min, the preparation temperature of emulsion is 85 DEG C~98 DEG C.

7. according to the method for claim 1, which is characterized in that step (A3) obtains the composition of emulsion are as follows: raw material wax Measuring percentage is 60.0%~90.0%, and the mass percent of water or salting liquid is 9.9%~30.0%, the mass percent of emulsifier It is 0.1%~10.0%.

8. according to the method for claim 7, which is characterized in that the composition of the emulsion are as follows: paraffin mass percent It is 65.0%~84.0%, the mass percent of water or salting liquid is 15.0%~30.0%, and the mass percent of emulsifier is 1.0% ~5.0%.

9. according to the method for claim 1, which is characterized in that force air flow through wax layer use described in step (B3) 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.

10. according to the method for claim 9, which is characterized in that force air flow through wax layer described in step (B3) and adopt Increase air pressure above wax layer to realize, applies the gauge of 0.2~2.0 atmospheric pressure above wax layer, and below wax layer Remain normal pressure.

11. according to the method for claim 9, which is characterized in that force air flow through wax layer described in step (B3) and adopt Air pressure is reduced below wax layer and realizes that air pressure keeps normal pressure above wax layer, and -0.2~-0.8 is maintained below wax layer The gauge of atmospheric pressure.

12. according to the method for claim 1, which is characterized in that proper temperature described in step (B2) is paraffin drop Fusing point~+2.0 DEG C of dropping point.

13. according to the method for claim 1, which is characterized in that cooling final temperature described in step (B2) is raw material 8 DEG C~15 DEG C below wax dropping point.

14. according to the method for claim 1, which is characterized in that force air flow through wax layer described in step (B3) and exist Sweating initial stage implements.

15. according to the method for claim 2, which is characterized in that the response type surfactant active is by organic acid and ammonia Water reaction, and Organic Alcohol is added and is made: organic acid and ammonium hydroxide is stirred to react 5 under conditions of 10~30 DEG C~it generates after sixty minutes Organic acid ammonium salt；Under conditions of 60~70 DEG C, Organic Alcohol is added into the organic acid ammonium salt prepared, stirring makes it in 5~30 minutes It is uniformly mixed to get response type surfactant active is arrived.

16. according to the method for claim 15, which is characterized in that the organic acid be the saturation that carbon number is 1~36 and Unsaturated acids.

17. according to the method for claim 16, which is characterized in that the organic acid is selected from caprylic acid, acid of the positive tenth of the twelve Earthly Branches, the positive last of the ten Heavenly stems Acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitinic acid, stearic acid, linoleic acid, oleic acid, nonadecanoic acid, peanut Acid, oxalic acid, malic acid, citric acid, maleic acid, fumaric acid constitute one or more of one group of substance.

18. according to the method for claim 15, which is characterized in that the mass concentration of the ammonium hydroxide is 1%~25%.

19. according to the method for claim 15, which is characterized in that the Organic Alcohol is saturation one of the carbon number 1~12 First alcohol.

20. according to the method for claim 1, which is characterized in that the sweatbox is sweating ware.

21. according to the method for claim 5, which is characterized in that the mass concentration of the salting liquid is 5%~20%.

22. according to the method for claim 9, which is characterized in that the pressure difference is 0.2~2.0 atmospheric pressure.

23. according to the method for claim 16, which is characterized in that the organic acid be carbon number 8~20 unitary or Multicomponent organic acid.

24. according to the method for claim 19, which is characterized in that the Organic Alcohol is methanol and/or ethyl alcohol.