KR890002559B1 - Latex emulsifiers - Google Patents

Abstract

An emulsifier for an emulsion polymerization is prepd. by the disproportionation and steam-spraying of a mixture of tall oil fatty acid and tall oil resin acid, and the distillation of at least main part of the mixture. The mixture contains 27-73% of fatty acid and 25-71% of resin acid.

Description

Latex Emulsifiers and Methods for Manufacturing the Same

The present invention relates to an improved emulsion polymerization emulsion and to an improved process for treating a mixture of a fatty acid and a resin acid found in a source of crude oil or distilled tall oil used in the emulsion polymerization. will be. Improved emulsifiers can be used to prepare polymers, such as synthetic rubber, by emulsion polymerizing monomers such as butadiene, styrene, and the like.

Tolu oil is a natural mixture of resinous acid and fatty acid non-saponifiable material. It is obtained by acidifying skimming black liquor when producing wood pulp by the sulphate method using wood with a lot of resin such as pine. The composition of the oil is somewhat dependent on factors such as the type of wood being pulped. Natural tolactic acids generally contain from 18% to 60% fatty acids, from 28% to 66% resinous acids and from 3% to 24% non-glycosylated substances. Natural tolactic acid may be used for the purpose of the present invention, but it is preferable to use distilled tol oil. Distillation can be carried out by introducing cheonanol oil into a fractional distillation unit to separate the volatile fractions of the natural earth oil from non-volatiles or pitches. In the first fraction, the oil distillate has almost the same composition as the natural tols, except for the separation of palmitic acid and more volatile acids. The oil distillate contains from 2% to 72% resin acid, from 27% to 73% fatty acid and from 3% to 12% non-gamine material. In addition to the mixed acid, a fatty acid to resin acid ratio comprising a fatty acid fraction and a resin acid fraction is used.

Several types of resin acids, such as abietic acid, palusteric acid, levopimaric acid and neoavietic acid, have conjugated double bonds, and therefore these resin acids have high chemical activity. Finally, it is known that the general polymerization is prevented when the alkali salt of the resin containing the resin acid is used as an emulsifier in the production of synthetic rubber. When rosin is used as an emulsifier for emulsion polymerization, it is necessary to convert a resin acid having a conjugated diene structure to a derivative thereof having no conjugated diene structure.

Polyunsaturated fatty acids such as linoleic acid, linolenic acid and eleostearic acid, like rosin, also have one or more double bonds in their respective molecular structures. It is known that the use of polyunsaturated fatty acids having active methylene between non-conjugated double bonds as an emulsifier for emulsion polymerization delays the polymerization reaction and prevents the normal progress of general polymerization.

When fatty acids are used as emulsion polymerization emulsifiers, fatty acids containing polyunsaturated fatty acids and mono-unsaturated fatty acids are often subjected to hydrogenation so that the mono-unsaturated fatty acids are often hydrogenated such that the reaction is carried out on polyunsaturated fatty acids and not on mono-unsaturated fatty acids. do. In order to obtain a suitable emulsifier, moderately moderate reaction conditions should be selected.

By disproportionation of earth oils, various proposals have been made to reduce large amounts of substances containing double bonds which are undesirable for free radical polymerization. In general, disproportionation is carried out by contacting the oil with the catalyst and heating it.

There are various processes conventionally regarding the disproportionation of fatty acids and / or resin acids in the presence of a catalyst. U.S. Patent 2,617,792 is a disproportionation reaction of a resin acid and a fatty acid mixture using a Nickel catalyst; US Pat. Nos. 2,407,248, 2,409,173, 2,494,550, 2,497,882, and 2,503,238 are sulfur catalysts (using disproportionation of rosin or polymerized rosin); U.S. Patents 2,311,386 and 2,503,268 have discovered a method of using iodine as a catalyst; U.S. Pat.No. 2,794,017 is an invention for producing linoleic acid moieties that can be easily polymerized by disproportionating the tooil using sulfur dioxide as a catalyst, and more recently US Pat. No. 3,980,630 to rosin, polyunsaturated fatty acids or mixtures thereof. It is to invent a method for producing an emulsion polymerization emulsifier consisting of a step of disproportionation reaction using an iodine catalyst, and then neutralizing the obtained product with an alkali such as KOH or NaOH.

脂) 지방산과 불균등화 목재수지비누에 대하여 동등한 중합성능을 부여하지 않으며, 어느 경우에는 물성에 약간 낮은 물질과 함께 고무가 생성된다.While the proposed method results in repositioning the double bonds, soaps prepared from disproportionated soil oils are partially hydrogenated-resins commonly used in emulsion polymerization.

Iii) It does not impart equal polymerization performance to fatty acid and disproportionated wood resin soap, and in some cases rubber is formed with a slightly lower material property.

The recessive rubbery material produced by the emulsion polymerization emulsifier obtained from the disproportionated soil oil has a lower latex particle size than the so-called partially hydrogenated resin, i.e., the resin acid emulsifier. Latex production and processing are improved by producing larger and more colloidal particles that are more stable. The problem usually caused by a small particle size is that (1) the coagulation increases and (2) the coagulation tack is larger. This may result in longer downtimes, as the latex manufacturer makes cleaning of the processing equipment more frequent and more difficult. One mechanism that can preferably increase the latex particle size is toe oil fatty acids that remain after disproportionation and pre-terminate the growth of individual polymers, or to oil oil fatty acids and to oil oil resins (natural or distilled oil). To remove trace amounts of impurities in the mixture. Presumably most of these impurities are phenolic residues from lignin, which have a boiling point in the oil range.

U.S. Patent 3,528,669 shows a method for removing these impurities by increasing the molecular weight by oligomerization (polymerization) reaction with a boron trifluoride catalyst. In this method, the natural or distilled toluene is first disproportionated to the extent that the acid content and the binolate acid content of the aviette form are reduced to less than 2% of the tolule. The product is heated at a temperature of 149 ° C. to 177 ° C. for 30 minutes to 1 hour in the presence of 0.01% to 2.0% of BF ₃ and then rapidly raised to 249 ° C. to 271 ° C. to prevent degradation of the product. For best results it was suggested to distill the BF ₃ treatment -product (redistillation if the starting product is a distillate of oil).

U.S. Patent 4,259,459 shows the treatment of ethanol, a mixture disproportionate with a fatty acid fatty acid and a resin acid found in natural or distilled earth oil in the presence of a catalyst such as iodine, H ₂ SO ₄ or p-toluene sulfonic acid. When the resulting product is used as an emulsion polymerization emulsifier, latexes having a particle size larger than that of the disproportionated oil fat and resin acid mixtures are not treated similarly. However, the use of aldehyde-treated and BF ₃ -treated emulsifiers for industrial use results in the formation of coagulum and increased tack resulting in undesirable consequences. It is therefore an object of the present invention to provide an improved emulsion polymerization emulsifier that reduces the formation and cohesion of coagulum. It is also an object of the present invention to provide an improved method for producing a pressure-sensitive adhesive.

Disproportionation of emulsifiers obtained from mixtures of fatty oil fatty acids with resinic acids, found in natural or distilled spirit oils, steam sparging and distillation result in large particle latexes, often pre-floc It has been found that coagulum called (pre-floc) forms in processing equipment such as butadiene blowdown tanks and styrene streaming colors. In fact, it has been found that these problems associated with latex production can be obtained by distilling at least the majority of the disproportionated mixture of oil fat and resin acid. Small amounts of emulsifiers can be similar mixtures that are not subjected to post- disproportionation distillation.

U. S. Patent 3,223, 696 shows a polymerization emulsifier prepared by either equalizing or dehydrogenating a rosin and then distilling the stabilized rosin. Distilled stabilized rosin can be used directly in emulsifiers for synthetic rubber preparation, but it is preferred to first mix it with a substantially neutral oil. However, there is no conventional method of representing the oil oil fatty acid and the rosin acid emulsion polymerization emulsifier prepared by distilling a mixture of the disproportionated fatty acid and the rosin acid.

In summary, the present invention is as follows.

The improved emulsion polymerization emulsifier is prepared by disproportionating the mixture of the oil fatty acid and the resin acid, then steam spurting the mixture, and then distilling at least most of the disproportionated product. The mixture of the oil-to-fatty acid and the resin acid may be prepared, or may be naturally obtained from natural or distilled oil.

Preferred specific embodiments are as follows.

In a preferred embodiment of the present invention, natural toe oil or toe oil distillate containing a mixture of fatty acid and resin acid is contacted with a catalyst and disproportionated by heating to a temperature of 160 ° C. to 271 ° C. for 1 to 4 hours. Of the several disproportionation catalysts described above, iodine is preferred and is used in amounts of 0.1 to 1.0%. In essence, during the disproportionation reaction, hydrogen is removed from several components and transferred to other components. The disproportionation product is a stabilized mixture of dehydrogenated and hydrogenated components.

After disproportionation, the mixture is steamed in a disproportionation reactor for up to 2 hours at the temperature near the disproportionation.

After disproportionation and steam sputtering, most of the disproportionation mixture of the oil fat and resin acid is distilled off. It is preferred to distill at least 75% of the disproportionation mixture. It is more preferable to distill 100% of the mixture with the inequality used as the emulsion polymerization emulsifier. In general, the relative proportions of resinic acids and fatty acids found in natural or distilled earth oils lead to disproportionation and subsequent distillation to produce the improved emulsion polymerized emulsifiers of the present invention. However, the mixed acid emulsifier preferably contains 30 to 70% of the resin acid. The improved mixed acid emulsifier preferably contains 40% resin acid.

A description of the practice of the invention is given in the following examples.

Example 1

12.51 kg of natural toe oil and 28.15 g of iodine (0.225%) were refined to contain about 28% resin acid, about 68% fatty acid, and about 4% non-glycosylated material.

The contents were then heated to reach the required disproportionation reaction temperature of about 485 ° F. after about 55 minutes. This temperature was maintained for 2 hours. At the end of this reaction the reactor contents were steam sputtered for 90 minutes. The disproportionated, steam sputtering product was about 30% resin acid.

The disproportionated, steam sputtered product 600 g was subjected to standard vacuum distillation under 0.1 mm Hg. After discarding about 10% (actually 9.77%) of headcuts and about 10% (actually 11.23%) of residues, about 80% (actually 79% or 473.4g) of distillate is emulsified with emulsion Created for use.

Example 2

Emulsified polymerization emulsifier was prepared by mixing the disproportionated, steam sputtered and distilled product of Example 1 with Westvaco Resin 95 at a ratio of 3: 1 to prepare a fatty acid fatty acid of about 40% resin acid. And a resinous acid mixture was produced. (Resin 95 is a distillation and equalization product of natural earth oil rosin) followed by the preparation of a latex with this emulsifier (M-40 ^* ), similarly to an emulsifier (M-40) which has not undergone post-unequalization distillation operations. And a "Plant mix" emulsifier control (prepared by mixing partially hydrogenated resin fatty acid and resin 95) to a 40% resin acid content. The prepared latex sample was evaluated for latex particle diameter, 6-hour conversion (% polymerized),% coagulum and tack. The results are shown in Table I.

TABLE I

There was no increase in particle size in the sample, but the 6-hour conversion, percent solids and tack improved.

Example 3

Similarly prepared plant disproportionated, laboratory distilled emulsifiers were used to disproportionate in the laboratory prepared in Example 2 and the evaluation of the distilled emulsifiers was repeated. The results are shown in Table II.

TABLE II

In this case, improvements were also made in the 6-hour conversion and coagulation percentage and tack as well as the particle diameter.

Example 4

The evaluations made in Examples 2 and 3 were repeated for emulsifiers prepared similarly to the above, using a plant disproportionated, plant distilled, oily fatty acid and resin acid mixture. The results are shown in Table III.

TABLE III

It was found again that all the properties evaluated were improved uniformly. While the present invention has been described and described in terms of various special materials and processes and implementations, it should be understood that the present invention is not limited to combinations and processes of special materials and materials selected for illustrative purposes. As will be appreciated by those skilled in the art, various modulations to the above details are possible.

Claims (12)

An improved process for the preparation of emulsion polymerized emulsifiers, characterized by consisting of disproportionation and steam sputtering of a mixture of toe fatty acids and toe oil resin acids followed by distillation of at least a majority of the mixture. A process according to claim 1, wherein the mixture of earth oil fatty acid and earth oil resin acid is selected from natural earth oil and earth oil distillate. The method of claim 1, wherein the mixture of the to oil fatty acid and the to oil oil acid is from about 27% to about 73% fatty acid and from about 25% to about 71% resin acid. The method of claim 1 wherein the toe oil fatty acid and the toe oil resin acid are about 60% fatty acid and about 40% resin acid. Emulsified polymerization emulsifier, characterized in that it comprises a mixture of a toe oil fatty acid and a toe oil resin acid treated in a discontinuous step of a sputtering step and then a step of distilling at least a majority of the mixture. 6. An emulsifier according to claim 5, wherein the mixture is selected from natural earth oils and earth oil distillates. 6. The emulsifier of claim 5 wherein the mixture comprises about 27% to 73% of toe oil and about 25 to 71% of a toe oil resinic acid. 6. The emulsifier of claim 5 wherein the mixture comprises about 60% of a fatty oil fatty acid and about 40% of a crude oil resin acid. In the method of polymerizing a monomer by emulsion polymerization, the emulsifier is a mixture of an oil-to-oil fatty acid and an oil-to-oil resin acid improved by treating the disproportionation and the steam sputtering step and the distillation step of at least the majority of the mixture. Emulsion polymerization method characterized by the above-mentioned. 10. The process according to claim 9, wherein the mixture of earth oil fatty acid and earth oil resin acid is selected from natural earth oil and earth oil deposit. 10. The process of claim 9, wherein the mixture of tol fatty acid and tol oil resin is from about 27% to about 73% fatty acid and from about 25% to about 71% resin acid. 10. The process according to claim 9, wherein the mixture of earth oil fatty acid and earth oil resin acid is about 60% fatty acid and about 40% resin acid.