CN1242019A - Adhesives with low level of residual monomers and process for manufacturing same - Google Patents

Abstract

An adhesive, which contains olefinic polymers and less than 1 % by weight of free monomers, is manufactured via catalytic hydrogenation. It is preferably used in the area of cosmetics, in the food sector, in medicinal plasters and transdermal systems.

Description

Tackiness agent that level of residual monomers is low and manufacture method thereof

The present invention relates to comprise the tackiness agent of polymkeric substance, wherein the amount of residual monomer is considerably less, the invention still further relates to their manufacture method and application thereof.

Say that typically adhesive tape, adhesive plaster etc. are with polymers soln or suspension is coated on the film or on the paper and make.Through super-dry organic solvent or moisture content are removed subsequently.The polyacrylic acid solution that is dissolved in organic solvent is particularly useful for this.These polyacrylate solution generally are by having vinyl-acetic ester concurrently under vinylformic acid, acrylate and some situation, adding for example Diisopropyl azodicarboxylate or other radical initiator, making through polymerization.After polyreaction or copolymerization are finished, add organic solvent diluting and be about 40% to solids content, this solution prepares to be used for coating afterwards.

Recently it has been recognized that this method has limitation, particularly under the situation of copolymerization, wherein active minimum monomer is difficult to participate in polyreaction.For this reason, the polymkeric substance of determining in order to obtain to repeat to prepare will use the excessive minimum monomer of this activity, as vinyl-acetic ester.In principle, the vinyl-acetic ester reaction is slower than acrylate, because the contained two keys of vinyl-acetic ester do not have and the carbonyl conjugation.The shortcoming that adds excessive vinyl-acetic ester is that the ratio of free vinyl-acetic ester in the solution is up to 7-8% with respect to solids content.Because the already mentioned diluting effect in front, this residual monomer content can reduce to about 3%.

Usually, in tackiness agent, especially at medicine, use in the cosmetic field and food product pack aspect in the tackiness agent that uses, do not meet the requirements at the residual monomer content of this order of magnitude.In addition, in many countries by legal provisions maximum residual monomer concentration.Therefore, carried out in the wide industrial field and be intended to reduce the activity of polymers soln residual polymer content that is used for aspect medicine and the food.

The method of known a kind of trial is extractive distillation.In this method, the former solvent of polymkeric substance in synthetic that be stored in almost all is removed.Because the physical properties (Buddhist point, vapor pressure) of vinyl-acetic ester and ethyl acetate only has minute differences, therefore necessary evaporate to dryness or constantly additional quilt steam the ethyl acetate of falling.Need experience very high temperature during evaporate to dryness, so that polymkeric substance is changed.Replenishing the ethyl acetate of being steamed and can cause a large amount of solvent consumptions, and form the waste of a large amount of solvents, is a kind of very expensive method.

The another kind of method of removing residual monomer is that the as lively as a cricket radical initiator of unconverted residual monomer and organo-peroxide class is reacted, and known this organo-peroxide can be used as a kind of scavenging agent.The defective of this method is that residual monomer is not removed, but reaction forms oligopolymer, still stays in the polymkeric substance.

Therefore, a kind of ideal method should have following advantage: the polymkeric substance that it produces should have the unconverted monomer or the oligopolymer of extremely low ratio; In the polymerization process or remove that thermal load should drop to minimum in the dissolving agent process; Only use a spot of organic solvent; Should avoid using scavenging agent; And should be economical.

Have now found that by means of the method for shortening, it is very low to make residual monomer content, has the polymer binder of above-mentioned advantage.

The tackiness agent that obtains comprises the polymkeric substance by the olefinic monomer preparation, and wherein residual monomer content is very low.These tackiness agents are applicable to the technical skill purposes, the sealing tape of using as office, or makeup, medicinal use, as be used for the manufacturing of adhesive plaster, electrode adhesive tape or transdermal therapeutic system.

Therefore, of the present invention is a kind of tackiness agent, and it comprises one or more polymkeric substance by the olefinic monomer preparation, wherein the content of free residual monomer is calculated by weight and is less than 1%, preferably is less than 0.3%, more preferably less than 0.02%, most preferably be less than 0.01%, but be no less than 0.0001%.

These polymkeric substance can be a kind of homopolymer, or the mixture of different homopolymer; The mixture of a kind of multipolymer or different copolymer thing; The mixture of a kind of block polymer or different block polymers; Or the mixture of one or more homopolymer, multipolymer or block polymer.Can comprise other materials according to tackiness agent of the present invention, adhesive resin for example is as staybelite fat; Yet they also can be made up of said polymkeric substance fully.

Present invention is specifically related to pressure sensitive adhesive, especially those contain one or more tackiness agents by the multipolymer of following monomer preparation: vinylformic acid, methacrylic acid, acrylate and methacrylic ester, wherein the ester group part can comprise nearly 8 carbon atom (C ₁-C ₈Alkyl), perhaps relate to the tackiness agent that those comprise the multipolymer of above-mentioned monomer and vinyl-acetic ester or styrene monomer.Suitable acrylate and methyl acrylic ester have methyl, ethyl, straight or branched propyl group, butyl, amyl group, hexyl, heptyl or octyl group ester, as ethylhexyl, or hydroxy ester, as the hydroxyl ethyl ester.

The present invention be more particularly directed to comprise the pressure sensitive adhesive of 2-EHA and vinyl acetate copolymer.

Another objectives of the present invention are the manufacture method that comprises the tackiness agent of one or more olefin polymers, and the content of its free monomers is calculated by weight and is less than 1%.This method comprises, after the polymerization of polymkeric substance or copolymerization were finished, this tackiness agent carried out hydrogenation reaction in the presence of heterogeneous or homogeneous catalyst in organic solvent.

Can use any suitable catalyzer, for example the palladium on platinum, palladium and the gac.The heterogeneous catalyst that is suitable for is palladium on the gac and the nickel on silica gel/aluminum oxide.A kind of suitable homogeneous catalyst is three (triphenylphosphine) rhodium chloride (I).

Hydrogenation process will carry out under the highest 150 ℃ temperature and under the hydrogen pressure of the highest 100 crust, preferred temperature is up to 100 ℃, the highest 80 crust of hydrogen pressure, and preferred temperature is the highest 100 ℃, hydrogen pressure is up to 52 crust, most preferably under room temperature and 1 pressure.

In any suitable organic solvent, especially can finish hydrogenation reaction in less than the organic solvent of water in polarity.Preferred solvent is an ethyl acetate.

These tackiness agents are very useful when the material requirements low residual monomer content, for example in transdermal therapeutic system and bandage, comprise in the transdermal system with cosmetic industry, and can be used for the tackiness agent of food product pack.These tackiness agents also can be used for medical proof fabric, comprise the medical proof fabric that the animal doctor uses.

Especially, the invention still further relates to the transdermal therapeutic system that contains tackiness agent according to the invention, especially a kind of pressure sensitive adhesive is as the multipolymer of 2-EHA and vinyl-acetic ester.This transdermal therapeutic system is made up of a kind of reservoir typically, wherein comprises d/d active agents, and by the adjacent layer made from the pressure sensitive adhesive of skin contact.

Yet in this system, pressure sensitive adhesive also can form single or multiple lift and hypothallus skin contact, therein active agents with dispersive or or even the dissolved form exist.If this matrix is multiwalled, each layer can be made up of different tackiness agents according to the invention.

In the alkene the two keys of C=C on platinum, palladium or charcoal palladium (Pd/c) or periodic system the 8th subgroup in other metals (as nickel) as in the presence of the catalyzer, under air pressure or higher hydrogen pressure, and under room temperature or high-temperature, carrying out shortening, this itself is early to be known.Yet, wish that it is impossible solving existing problem by this well-known method of hydrotreating of application, because this method has to carry out under worst condition.

Before hydrogenation, for example, the concentration of residual monomer very low (＜3%).In addition, will see that if the polarity of solvent of using is very weak, it is particularly unfavorable to carry out hydrogenation with metal catalyst as us.Because the hydrogenation reaction of carrying out after the polyreaction is to carry out under the condition that is non-polar organic solvent such as ethyl acetate basically, this means that reaction conditions is particularly unfavorable.However, the method for the application of the invention, the content of residual monomer can successfully reduce to below 0.3%, even can be low to moderate 0.01%.

This is not the inference in a past, and this point is by United States Patent (USP) 4,375, and 529 ((Fong etc.) have confirmed.This patent has been described a kind of method that reduces residual monomer content in the water-fat liquor that contains partially polymerized acrylamide and sodium acrylate.Amounting at the described extent of polymerization of this patent is 80% only, this means that the concentration total of residual monomer is about 20%.

Hydrogenation subsequently carries out in water, and this is a kind of high polar solvent.Allow to use very high pressure simultaneously.But the concentration of resulting residual monomer also is about 1% under best situation, also can reach such level by means of the polymerization technique that is fit to.Because the reason pointed out above, these numerical value be Tai Gao and can not being accepted still.

According to method of the present invention, in the presence of metal catalyst, be up under 150 ℃ the temperature, be preferably the highlyest 100 ℃, and under the pressure of 0.3 crust～100 crust, be preferably 0.5 crust～80 crust, in organic solvent, binder solution is carried out hydrogenation.

Particularly preferred method is at platinum, palladium or in the presence of the palladium on the charcoal, carries out hydrogenation under the hydrogen pressure of room temperature and an air pressure.According to method of the present invention also can be in periodic system in the 8th subgroup other metals such as nickel carry out under the hydrogen pressure of higher temperature and Geng Gao as in the presence of the catalyzer.

Preferred solvent is that those are than aqueous polar low (being that those specific inductivity are less than water) solvent.A kind of preferred solvent is an ethyl acetate.

Should be realized that in transdermal therapeutic system, be present in any unreacted monomer in the tackiness agent or initiators for polymerization by product and with transdermal system in will d/d medicine the material that reacts tendency to be arranged all be undesirable.Therefore, can reduce the content of residual monomer in the tackiness agent or other reactive compounds, reach alap degree, an one significantly benefit is can be applied in such treatment system.

Moreover, use the ethyl acetate of hydrogen addition technology generation, thereby can reduce the content of vinyl-acetic ester as product.Because ethyl acetate often is selected as the solvent of tackiness agent, so there is not new component to add in the binder matrix.

The following example will be used for further specifying the present invention, but can not regard it as limitation of the present invention.Employed detection step is described to some extent in the technological process part of embodiment back among the explanation of hydrogenation reaction and the embodiment.

Embodiment

The hydrogenation reaction of embodiment 1. vinyl acetate ester formulations.Being formulated in ethyl acetate solid content by the multipolymer of vinyl-acetic ester, vinylformic acid 2-hydroxyl ethyl ester (2-HEA), 2-EHA (2-EHA) and glycidyl methacrylate preparation is 10% solution, hydrogenation under as the condition of table 1, catalyst levels is 10% of a solution weight, measures vinyl acetate monomer (VAM) residual content then.Although only at room temperature with the mild conditions of a pressure hydrogen down and use palladium catalyst on gac, data show that remaining vinyl-acetic ester has reduced.Though these data show that also the nickel catalyzator that carries is inoperative under mild conditions, it is effective under the comparison intensive condition of 80 ℃ and 52 Ba Qing.There is not experimental results show that of hydrogen: not only have vinyl-acetic ester to be adsorbed on the charcoal of catalyzer, in fact, reduction reaction has taken place also.Although used Utopian condition, 10% polymer solids and 10% catalyst loadings, these experiments show: for specific catalyst, its condition is after optimizing, no matter use palladium or Ni-based catalyzer to carry out catalytic reduction, the residual content of vinyl acetate monomer is descended.Preferred catalyzer is a palladium catalyst.

Table 1

Hydrogenation is to the influence of vinyl acetate monomer (VAM) content

Catalyzer (polymers soln weight 10%)	Hydroconversion condition	VAM content e
				Before the reduction	After the reduction
		5％Pd/C a	Room temperature, 1 normal atmosphere H 2 d, 16 hours			17,700	＜220
?55％Ni/Si b	Room temperature, 1 normal atmosphere H 2, 16 hours			17,700	?16,500
		?5％Pd/C	Room temperature, no H 2, 16 hours			17,700	?16,500
?55％Ni/Si	50 ℃, 52 crust H 2, 14 hours			36,000	?40,000
		?65％Ni/Si/Al c	50 ℃, 52 crust H 2, 14 hours			42,000	?16,000
?65％Ni/Si/Al	80 ℃, 52 crust H 2, 14 hours			34,700	?350

Remarks: the palladium on a. gac

B. the nickel on the silica gel

C. the nickel on silica gel/aluminum oxide

D. room temperature, 1 atmospheric pressure hydrogen

E. be 100% calculating by polymer solids

Embodiment 2. uses the more effect of high polymers solids content hydrogenation.Whether experiment in this embodiment is intended to measure when being higher than 10% solid matter can reduce.Hydrogenation be with embodiment 1 in employed identical multipolymer be to carry out under the hydroconversion conditions of 52 crust at 80 ℃ and hydrogen pressure, use the catalyzer that 5% palladium is arranged on the gac, perhaps with the catalyzer that 65% nickel is arranged on silica gel/aluminum oxide, the amount of catalyzer is 10% of a polymers soln weight.The results are shown among the table 2a.Show that when carrying out this reaction under any concentration below the highest at least about 50% solid the amount of residue VAM can reduce to the level that is lower than 1000ppm.

Table 2a

The variation of solid polymer amount

Catalyzer (polymers soln weight 10%)	The solid polymer amount, %	VAM content before the reduction, ppm a	Reduction back VAM content, ppm a
				Pd/C	?10	?16,500	＜220
Room temperature, 1 normal atmosphere H 2	?25	?17,900	＜200
				16 hours	?50	?18,700	＜110
?65％Ni/Si/Al	?10	?34,700	?350
				80 ℃, 52 crust H 2, 16 hours	?50	?33,800	＜110

Remarks: a. is 100% calculating by polymer solids

This is very important, significantly increases along with solid percentage ratio in the preparation because table 2b demonstrates the viscosity of matrix.Therefore showing data among the 2a, to further specify in very sticking matrix hydrogenation still effective.

Table 2b

Viscosity table

Solid, %	Viscosity, cp
		????51.5	????22500
????40	????2700
		????35	????1240
????30	????580
		????25	????290

Embodiment 3. hydrogenation are to the influence of other residual monomers.Use with embodiment 1 in identical multipolymer after hydrogenation, carry out the test of other monomers existence except that vinyl-acetic ester.But unique monomer that reaches detection level is 2-EHA; May there be remaining 2-HEA and GMA, but be lower than the detectable limit.The results are shown in table 3.It shows that remaining acrylate also reduces when making the minimizing of residual acetic acid vinyl acetate when using described hydroconversion condition.

Table 3

Hydrogenation is to the influence of 2-HEA

Hydroconversion condition	2-HEA before the reduction	2-HEA after the reduction
			50% polymer solids, 5% Pd/C during 10% polymers soln, room temperature, 1 atmospheric H 2, 16 hours	48ppm	＜20ppm
10% polymer solids, 65% Ni/Si/Al during 10% polymers soln, 80 ℃, the H of 52 crust 2, 16 hours	44ppm	＜5ppm

The hydrogenation of embodiment 4. all acrylic ester preparations.Be prepared into all acrylic ester multipolymer by 2-EHA (2-EHA), methyl acrylate, vinylformic acid and glycidyl methacrylate, be dissolved in the mixing solutions of 54% ethyl acetate, 34.6% Virahol and 11.4% hexane, be mixed with 37% polymer solids.It is to carry out hydrogenation under 52 conditions of clinging at 80 ℃ with hydrogen pressure that this polymers soln uses the catalyzer that contains 65% nickel on silica gel/aluminum oxide.The results are shown in table 4.It shows uses described hydroconversion condition, and remaining acrylate monomer can reduce significantly.Table 4

Sample	Monomer concentration, ppm
					Vinylformic acid 2-(ethyl hexyl) ester	Methyl acrylate	Vinylformic acid	Glycidyl methacrylate
	Before the reduction	?7,360	?＜200	?920					＜200
After the reduction					?＜75	?＜200	?50	＜200

Embodiment 5. uses the amount of catalyzer and residual catalyst.Consider that from economic reasons and from being easy to remove catalyzer catalyst content is low as far as possible to be favourable.

(a) in this embodiment, use to contain 5% Pd on the gac and carry out hydrogenation reaction, catalyst levels is reduced to 0.05%～0.1% of polymers soln weight.Copolymer compositions is employed in embodiment 1, and polymers soln has 50% solids content.Before hydroconversion condition and the hydrogenation and hydrogenation residual ethylene acetic ester monomer content afterwards list in the table 5.Even it is that 0.05% o'clock hydrogenation also is highly effective that the result shows at catalyst content.

In order to measure the content of residue Pd, the polymers soln that is reduced removes by filter catalyzer, by the remaining Pd content of atomic absorption test determination.Use 3.0 μ mMillipore filter paper 4 the crust and 60 ℃ under filter.Four samples in the table 5 all show Pd content very low (＜2ppm).Stay one of them sample and placed for 2 weeks, filter and analyze Pd content then.The sample of direct filtration is compared after this sample and those hydrogenation, and its Pd content does not significantly increase.Four sample hydrogenation color and hydrogenation not changes of color of polymkeric substance before afterwards.The results are shown in Table 5.

Table 5

The content of 5%Pd/C catalyzer

Catalyst content by the percentage ratio calculating that accounts for polymers soln	60 ℃ of hydroconversion conditions, 52 crust H 2	Residual VAM, ppm		Filter the residual Pd in back, ppm
					Before the reduction	After the reduction
		?0.1	1 hour				16000	＜50	＜0.1
?0.1	1 hour			16000	＜50	1.5
		?0.05	3 hours				16000	＜50	0.4
?0.1	1 hour			16000	＜50	1.1, place 2 all after-filtration

Millipore filter paper with 5.0 μ m and 1.0 μ m filters in addition.5.0 it is bad that μ m filter paper is removed catalyst effect, but (Celite) plastic gasket can improve filtration capacity in the top plug adding on the paper.1.0 μ m filter paper 60 ℃ and the highest 8 the crust nitrogen pressures under polymers soln or catalyzer are passed through.In order to test actual filtration by the technical scale magnification ratio, under 60 ℃ and 7 crust, on commercially available filter paper, to filter with identical sample, discovery can be removed catalyzer effectively.

(b) remaining Ni catalyzer.Under 52 crust hydrogen pressures and 80 ℃, use the catalyzer that contains 65% nickel on silica gel/aluminum oxide to carry out hydrogenation with heap(ed) capacity with respect to polymers soln weight 10%.Remaining VAM is 55ppm by the calculating of 50% solid in this sample, calculates by 50% solid in ethyl acetate, and the content of nickel is 5.1ppm.

Embodiment 6. usefulness large granular catalysts carry out hydrogenation.Among the embodiment in front, used catalyzer is a powdery, though reduction effect is fine, needs powder is filtered out from polymers soln when hydrogenation finishes, and has increased an extra step to present method.In order to remove filtration from, adopt oarse-grained catalyzer in the hydrogenation reaction in the present embodiment.These catalyzer are coccoid or shred, are suspended in the Metal net basket in the reactor, and the mixing lodicule that reactor is set makes polymer solution flow pass through the position of this basket.This application method of the catalyzer that particle size is big is that imitation is used for for example commercially available fixed bed system of continuous hydrogenation equipment.

Use two kinds of different catalyzer: containing 0.50% palladium on the 3.2mm alumina globule and on 4 * 8 order carbon plates, containing 1.0% palladium.All reactions all are in the polymers soln that contains 50% polymer solids, carry out under the temperature and time that indicates in 48 crust hydrogen pressures and table 6.The multipolymer that uses is identical with the multipolymer among the embodiment 1.As what from these data, seen, adopt the big catalyzer of particle size can realize hydrogenation.

Table 6

Condition		Catalyzer		VAM *Content, ppm
						Hour	℃	Composition	Shape	Before the reduction	After the reduction
70	?35-45	?0.5％Pd/Al	3.2 mm granules	2700	＜10
						?4	?35-45	?0.5％Pd/Al	3.2 mm granules	2700	?25
?2	?35-45	?0.5％Pd/Al	3.2 mm granules	3150	?1340
						?2	?50	?1.0％Pd/C	4 * 8 sieve meshes	3400	＜24

^*All monomer concentrations all calculate according to the solution of 10% solid content, and the monomer concentration that calculates according to solids content 100% should multiply by the factor 10

Embodiment 7. usefulness homogeneous catalysts carry out hydrogenation.In the embodiment of front, being done, in hydrogenation process, when using heterogeneous catalyst, generally to after finishing, hydrogenation remove by filter catalyzer.When using homogeneous catalyst, because the amount of catalyst system therefor is considerably less, it can be stayed in the solution, thereby remove filtering step from.This makes present method more effective.Using the amount that contains the residual acetic acid vinyl acetate among a kind of homogeneous catalyst hydrogenation embodiment 1 in this embodiment approximately is the polymers soln of 16000ppm, various homogeneous catalysts all are to know and use always in the field of hydrogenation, and they can be applied in the method for hydrotreating described in the invention.

The special in this embodiment catalyzer that uses is the Wilkinson catalyzer, and three (triphenylphosphine) rhodium chloride (I) is pressed the sample total weight, and its consumption is 1ppm (approximately containing the 0.1ppm rhodium).Carry out 16 hours hydrogenation reaction 60 ℃ the time with 48 crust hydrogen.Remaining vinyl acetate monomer content remains unchanged.Carry out this hydrogenation reaction of reforming in 16 hours 60 ℃ the time with 48 crust hydrogen, use 10ppm Wilkson catalyzer (approximately containing the 1ppm rhodium).In second experiment, remaining VAM reduces to 2900ppm from 16200ppm.

The hydrogenation of embodiment 8. residue initiators.In order to test the hydrogenation effect of the residual polymer initiator that is present in the polymers soln, the pressure-sensitive polymer sample that will contain the remaining benzoyl peroxide of 250ppm, in the time of 60 ℃, under the 48 crust hydrogen pressures, to contain the catalyzer of 5% palladium on the amount adding gac of every part of polymer solids to 0.05 weight percentage catalyzer, carry out 16 hours hydrogenation reactions.After the hydrogenation sample is analyzed, shown not detect benzoyl peroxide.

Technological process

Detect the method for residual monomer.

Use external standard to carry out the direct injection vapor-phase chromatography is carried out residual monomer or by-products content before hydrogenation and after the hydrogenation to each preparation test with Hewlett-Packard 5890 GC/FID.Testing used chromatographic condition is:

DB-624 of gas chromatographic column: 30m * 0.35mm internal diameter (3 μ m film) or coordinator

Stove: 45 ℃ following 5 minutes, rise to 230 ℃ with 30 ℃/min speed

Injection compartment: 180 ℃

Detector: 275 ℃

Carrier gas: helium, 8ml/min

Use heterogeneous catalyst to carry out hydrogenation

Employed copolymer sample 1000g among the embodiment 1 made in ethyl acetate contain about 50% solid solution and join in the 2000ml Parr pressure reactor, add the powdered catalyst of the palladium (5%Pd) on the 0.5g gac.With the reactor sealing, with the purging with nitrogen gas twice of 14 crust,, in reactor, be pressed into 48 crust hydrogen, and be heated to 60 ℃ then with the hydrogen purge twice of 35 crust, wherein pressure is increased to about 52 crust.In the time of 60 ℃, the rotating speed of reaction mixture with 1000 rev/mins stirred 1 hour then.After the cooling, give the pressurized vessel exhaust, add ethyl acetate and be about 10-15% with diluted mixture thing to solids content.Catalyzer is removed through filtering with 45 μ m injection filters.

Use homogeneous catalyst to carry out hydrogenation

25% solution example of the multipolymer among the 200g embodiment 1 is joined in the 2000ml Parr voltage-resistant reactor, add the standardized solution (amount in ethyl acetate is 0.20mg/ml) of 10ml Wilkinson catalyzer.With this reactor sealing, with 28 crust purging with nitrogen gas twice, cling to the hydrogen purges twice then with 35.Be pressed into 44 crust hydrogen in reactor, and be heated to 60 ℃, its pressure is increased to about 48 crust.In the time of 60 ℃, the rotating speed of reaction mixture with 1000 rev/mins stirred 1 hour then.After the cooling, exit to pressure vessel.

Pressure filtration

Use a kind of Millipore type pressure filter (Millipore#YT30142HW142mm refuse filtration system) from polymers soln, to filter powdered catalyst on a large scale.Through after the hydrogenation experiment, this reactor is not emptied completely, cooling polymer solution not yet.With hydrogen discharge to 7 crust, this device is forced into 21 crust again with nitrogen; This process repeats twice or is manyly replaced by nitrogen up to hydrogen.Under the 7-8 bar pressure, under about 50-60 ℃ temperature, directly reaction mixture is discharged in the strainer then through suction pipe.The temperature reading of the polymers soln that comes out from strainer is approximately 40 ℃.Use the heating zone around the strainer so that in whole filtration procedure middle filtrator insulation.

Claims (26)

1. a tackiness agent comprises one or more olefin polymers, and by weight, free monomer wherein is less than 1%.

2. according to the tackiness agent of claim 1, by weight, free monomer content wherein is less than 0.3%.

3. according to the tackiness agent of claim 1, by weight, free monomer content wherein is less than 0.02%.

4. according to the tackiness agent of claim 1, by weight, free monomer content wherein is less than 0.01%.

5. according to the tackiness agent of claim 1, polymkeric substance wherein is the mixture of homopolymer or different homopolymer.

6. according to the tackiness agent of claim 1, polymkeric substance wherein is the mixture of multipolymer or different copolymer thing.

7. according to the tackiness agent of claim 1, polymkeric substance wherein is the mixture of block polymer or different block polymers.

8. according to the tackiness agent of claim 1, polymkeric substance wherein is to be selected from homopolymer, multipolymer, block polymer and their mixture.

9. according to the tackiness agent of claim 1, it is characterized by and have pressure sensitive quality.

10. according to the tackiness agent of claim 9, one kind of or multiple polymers is by being selected from vinylformic acid, methacrylic acid, vinylformic acid C ₁-C ₈Alkyl ester and methacrylic acid C ₁-C ₈Alkyl ester monomer is prepared from.

11. according to the tackiness agent of claim 9, wherein one or more polymkeric substance are by being selected from vinylformic acid, methacrylic acid, vinylformic acid C ₁-C ₈Alkyl ester, methacrylic acid C ₁-C ₈Alkyl ester, vinyl-acetic ester and styrene monomer are prepared from.

12. according to the tackiness agent of claim 11, polymkeric substance wherein is the multipolymer of 2-EHA and vinyl-acetic ester.

13. a method for preparing by the tackiness agent of claim 1 is included in after one or more polymer polymerizings or the copolymerization fully, and the tackiness agent in organic solvent is carried out hydrogenation reaction in the presence of homogeneous phase or heterogeneous catalyst.

14. according to the method for claim 13, catalyzer wherein is a heterogeneous catalyst, i.e. palladium on gac.

15. according to the method for claim 13, catalyzer wherein is a heterogeneous catalyst, i.e. nickel on silica gel/aluminum oxide.

16. according to the method for claim 13, catalyzer wherein is a homogeneous catalyst, i.e. three (triphenylphosphine) rhodium chloride (I).

17. according to the method for claim 13, wherein hydrogenation reaction is up to 150 ℃ and hydrogen pressure in temperature and is up under 100 crust and carries out.

18. according to the method for claim 13, wherein hydrogenation reaction is up to 100 ℃ and hydrogen pressure in temperature and is up under 80 crust and carries out.

19. according to the method for claim 13, wherein hydrogenation reaction is up to 100 ℃ and hydrogen pressure in temperature and is up under 52 crust and carries out.

20. according to the method for claim 13, wherein hydrogenation reaction is to be room temperature and under an air pressure in temperature, carries out in the presence of the catalyzer such as (Pd/C) of the palladium on platinum, palladium or the charcoal.

21. according to the method for claim 13, organic solvent wherein is littler than the polarity of water.

22. according to the method for claim 21, organic solvent wherein is an ethyl acetate.

23. a transdermal therapeutic system comprises the tackiness agent according to claim 1.

24. a medical or animal doctor uses adhesive plaster, comprises the tackiness agent by claim 1.

25. according to the tackiness agent of claim 1 makeup, food product pack or medical or animal doctor with Application for Field such as adhesive plasters.

26. the application of tackiness agent in transdermal system according to claim 1.