US3716547A

US3716547A - Process for the preparation of a poly(vinyl acetate-dialkyl maleaee-acrylic acid) textile sizes

Info

Publication number: US3716547A
Application number: US00098914A
Authority: US
Inventors: A Corey; D Donermeyer; J Fantl; C Williams
Original assignee: Monsanto Co
Current assignee: Monsanto Co
Priority date: 1970-12-16
Filing date: 1970-12-16
Publication date: 1973-02-13
Anticipated expiration: 1990-02-13
Also published as: DE2162285A1; GB1335586A; US3854990A; US3832321A; US3817892A; US3723381A

Abstract

Disclosed herein is a process for the preparation of a poly(vinyl acetate-dialkyl maleate-acrylic acid) textile size which comprises (1) interpolymerizing the monomers at a temperature of from 40* to 60*C. to form a latex using a surfactant system comprising a phosphate ester of an alkyl phenolethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms; and (2) dissolving the resulting latex in a basic aqueous medium to form the size.

Description

United States Patent 1191 Corey et al. C

' Assignee:

PROCESS FOR THE PREPARATION OF A POLYWINYL ACETATE-DIALKYL MALEAEE-ACRYLIC ACID) TEXTILE SIZES lnventors: Albert E. Corey, East Longmeadow; Donald D. Donermeyer; Joel Fantl, both of Springfield; Charles R. Williams, Longmeadow, all of Mass.

Monsanto Company, St. Louis, Mo.

Filed: Dec. 16, 1970 Appl. No.: 98,914

U5. c1 ..260/29.6 TA, 260/29.6 MN, 260/29.6 MP,

260/785 T, 117/138.8 R, 117/1395 A, 117/161 uc, 117/161 ur, 117/161 uz I m. 01. ..,,,gq 1 y1 1) o 6c37/0o i iidii'r' s66r611 ..260/29.6 Mi 29.6 MN, 29.6 TA, 78.5 T

Feb. 13, 1973 [56] References Clted UNITED STATES PATENTS 2,853,471 9/1958 Beadell ..260/29.6 MP 3,231,534 l/1966 Blades et al ..260/29.6 TA 3,449,282 6/1969 Lasher et al. .......260/29.6 MP

Primary Examiner-William H. Short Assistant Examiner-L. M. Phynes Attorney-William .1. Farrington, James C. Logomasini, Neal E. Willis and Richard W Sternberg [57] ABSTRACT 17 Claims, No Drawings PROCESS FOR THE PREPARATION OF A POLY(VINYL ACETATE-DIALKYL MALEAEE- ACRYLIC ACID) TEXTILE SIZES BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for the preparation of textile sizes. More particularly, it relates to a process for the latex polymerization of a poly(vinyl acetate-dialkyl maleate-acrylic acid) textile size wherein the dialkyl maleate is selected from the group consisting of dimethyl maleate and diethyl maleate, wherein the resulting latex is dissolved in a solvent to form the size.

2. The Prior Art Polymeric substances are well known in the prior art for use as textile sizes. In conventional loom operations yarn is sized with an aqueous solution of a water soluble material such as a copolymer of vinyl acetate and carboxylic acid, woven into cloth on a conventional loom with a mechanical shuttle and then the size is removed in a water bath. While these sizes have been adequate in the past, recent developments in the textile industry have created an increasing demand for textile sizes with improved tensile strength, elongation, toughness, solubility characteristics, etc.

One such development in recent years is the water jet loom. The water jet loom employs a jet of water in place of a mechanical shuttle in order to weave the yarn into a fabric. A water jet loom provides a faster weaving operation and less mechanical abrasion of the yarn. The result is an increase in production and improved quality in the woven fabric.

The size used in water jet weaving operations is customarily applied from aqueous solution. Once it is applied to the yarn and dried, the size must be sufficiently water resistant so as to remain on the yarn during the weaving operation. Moreover, in order to be efficient and effective, the size must retain its adhesion and film properties such as high tensile strength when wet by the water jets in the weaving process without becoming soft and slimy. Finally, the size must be soluble in mild aqueous alkali solutions or organic solvents so that it can be removed from the woven fabric. The foregoing properties are the result of a critical interrelationship between chemical composition and molecular weight of the polymeric material which is used as the textile size.

The sizes ofthe prior art which are customarily used in conventional loom weaving operations are found to lack the necessary physical properties which are required for use with water jet looms.

Thus, there exists in the art a need for a process for the preparation of improved textile sizes which can be used to size yarns which are to be woven on conventional or water jet looms then removed using either an aqueous alkali solution or an organic solvent.

SUMMARY OF THE INVENTION The above-mentioned need in the prior art is fulfilled by the present invention which provides a process for the preparation of textile sizes which are suitable for use on both conventional and water jet looms. More particularly, the present invention provides a process for the preparation of a textile size which process comprises (l) interpolymerizing critical amounts of vinyl acetate, dialkyl maleate and acrylic acid monomers in a latex system at a temperature in the range of from 40 to 60C. in the presence of a surfactant system comprising a phosphate ester of an alkyl phenol-ethylene oxide condensate; dissolving the resulting latex in an aqueous or organic solvent to form the size.

The polymers prepared in accordance with the processes of the present invention have excellent solubility characteristics and film properties. Moreover, sizes prepared from these polymers are easily removed from sized yarns or the resulting fabric using aqueous alkali solutions or organic solvents. Consequently, these polymers are especially suitable for use as yarn warp sizes for use on conventional or water jet looms.

THE PREFERRED EMBODIMENTS The monomers used in the interpolymerization processes of the present invention are vinyl acetate, a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and acrylic acid. The polymerization charge comprises from 83 to percent by weight of vinyl acetate, from 2 to 10 percent by weight of dialkyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers. More preferably, the polymerization charge comprises from 87.5 to 9l percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of dialkyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers.

The latex polymerization process of the present invention is carried out at a temperature in the range of from 40 to 60C. and preferably at a temperature in the range of from 40 to 45C. At temperatures below about 40C. the polymerization rate is too slow and the reaction mass tends to coagulate. At polymerization temperatures above 60C. the product is of low molecular weight and lacks the tensile strength and elongation required in sizes for use on water jet looms.

The surfactant system used in the processes of the present invention comprises a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains from seven to 11 carbon atoms. Especially preferred are the phosphate esters of tertiary octyl phenol-ethylene oxide condensates (hereinafter referred to as PEOPEO) and the phosphate esters of nonyl phenol-ethylene oxide condensates (PENPEO). These preferred surfactants are available commercially as Triton XQS (Rohm & Haas Company) and GAFAC RE-870 (General Aniline & Film Company), respectively. The amount of the phosphate ester of an alkyl phenol-ethylene oxide condensate used in the present invention will be in the range of from 1.0 to 4.0 percent by weight based on the total weight of the latex.

Preferably, the polymerization processes of the present invention are carried out using an anionic cosurfactant in combination with the phosphate esters of an alkyl phenol-ethylene oxide condensate. The use of the co-surfactants reduces the amount of coagulum in the resulting latex and provides a better product. The preferred co-surfactants used in the present invention include alkyl aryl sulfonates such as sodium dodecyl, benzene sulfonate; fatty alcohol sulfates such as sodium lauryl sulfate; dialkyl sulfosuccinates, sodium dihexyl sulfosuccinate; etc.

The amount of co-surfactant used is in the range of PART A PREPARATION OF LATTCES 0.1 to 0.3 percent by weight and more preferably 0.15 to 0.25 percent by weight based on the total weight of EXAMPLE 1 the latex.

The polymerization processes of the present invention are initiated by a two component redox free radical initiator system. Suitable oxidizing components for A latex is prepared in conventional latex polymerization equipment while maintaining a nitrogen atmosphere and mild agitation using the following the system are the inorganic peracid salts such as amcharge.

monium, potassium and sodium persulfates, perborates, and hydrogen peroxide. Preferred however, CHARGE PARTS are the oil soluble organic hydroperoxides such as t- A. wa 0 (15251153 butyl hydroperoxide cumene hydroperoxide, p- Ammonium hydroxide (28%) 010 menthane hydroperoxrde, etc. and esters of the t-butyl sodium formaldehyde sulfoxylate 0.05

perbenzoate type. The useful reducing components in Hwy] Y mxide (90%) 7 0m clude compounds like the sulfites, bisulfites, Dimmy ma eamwMMy L75 hydrosulfites and thiosulfites; ethyl and other alkyl VIIIYIACWWWOAC) 31.67

Acrylic Acid 1.58

sulfites; the sulfoxylates, such as sodium formaldehyde sulfoxylate; and the like. Especially preferred are initiator systems based on t-butyl hydroperoxide and sodium formaldehyde sulfoxylate; and redox combinations such as mixtures of hydrogen peroxide and an iron salt, hydrogen peroxide and zinc formaldehyde sulfoxylate or other similar reducing agent; hydrogen peroxide and a titanous salt; potassium persulfate and sodium bisulfate and a bromate mixed with a bisulfate.

The use of equimolar amounts of initiator system components is generally preferred although the amount of each component as well as the total amount of catalyst used depends on the type of component used as well as on other polymerization conditions and may range between 0.02 and 0.2 percent by weight of the total polymerization system, the preferred range being 0.02 to 0.06 percent for the oxidizing component and 0.04 to 0.1 for the reducing component. v

The solids contents of the latices prepared by the reslm has a 3 ifi z f ig processes of the present invention can be varied over a 2) percent P y a wide "Inga The preferred latices having a solids com ther properties of this latex are tabulated in Table I .tent in the range of from 15 to 65 percent by weight below and more preferably from 35 to 55 percent by weight, based on the total weight of the latex. EXAMPLES 2 to 10 During the polymerization-reaction a conventional The PEOPEO surfactant, ammonium hydroxide 20 buffer solution, sodium formaldehyde sulfoxylate and the water are charged to a glass lined reaction vessel. The tertiary butyl hydroperoxide polymerization initiator is dissolved in the monomeric mixture and eight percent (8 percent) of the monomeric change (charge 25 B) is then dispersed in the charge A. The remaining 92 percent of the monomers (charge B) is added to the reaction vessel by a conventional delayed addition technique over a period of 2% hours. During this time the temperature of the reaction batch is maintained in the range of from 41 to C. while maintaining mild agitation.

The resulting latex has a total solids of 35.7 percent, a pH of 4.9 and a Brookfield viscosity of 23 centipoises. The poly(vinyl acetate-dimethyl maleate-acrylic acid) b h as ammgnium h d id or di h d The following Examples 2 to 10 are set forth to illuside is d to b ff th latex to i th range f 4,0 trate variations in the latex polymerization reaction to 6,0, 5 conditions of the present invention. In each case the The following examples are set forth in illustration of general procedures of Example 1 are followed except the present invention and should not be construed as a for the noted changes. The resulting latices have solids limitation thereof. Unless otherwise indicated, all parts contents in the range of from 35 to 42 percent by and percentages given are by weight and polymerizaweight and Brookfield viscosities in the range of from tion temperatures are maintained in the range of from 10 to 50 c at 25C, Th examples r t bulat d i 41 to 45C. the following Table 1. I

TABLE IQ-SUMMAIZY OFTEXAMPQLES 1 To 10 Example 1 2 3 4 5 6 7 8 9 10 Charge A Water 62 03 57 7 57 87 62 03 62.03 57 62. 03 57 03 62. 03 57 70 PEOPEO 1 68 1 58 1.58 1. 26 1 58 1. 58 PENPEO 1 58 1.58 1.58 1.58 0 20 0. 20 0 20 0. 25 0. 20 0. 2O 0 20 0 20 0. 20 NHiOH (28%).--- 0 20 0 39 0. 39 0 20 0. 20 0 39 0 20 0 39 a 0 18 0. 18 Charge B:

Total monomer 35 40. 0 40. O 35. 0 35. 0 40. 0 35 4c 35 40 Percent vinyl acetate 90. 5 86. 65 91. 65 Q0. 5 86. 5 90. 5 90. 5 89 5 90. 5 00. 5 Percent dialkyl maleate 5. 0 10. 0 5. 0 5. 0 7. 5 5. 0 5. 0 5 0 5. 0 5. 0 Percent acrylic acid 4. 5 3. 36 3. 35 4. 5 0. 0 4 5 4. 5 5 5 4 5 4.5 Percent total eoagul'um 0. 68 0. 02 0. 16 0. 2 0 05 0 15 0. 08 0 07 0 04 Polymer properties:

Specific viscosity 2. 51 1. 38 1- 64 2. 31 2. 93 2. 2. 92 6. 05 2. 78 2. 58 Tensile/percent elongation:

Dry 65 R.H 3, /2S8 5, /110 2,350/380 2, 000/283 2, /320 3, 320/370 3, 560/423 3, 040/360 1, 770/442 2, 030/310 1. 530/430 .2, 310/541 720/590 2, 000/574 1, 440/470 1n the foregoing Table I percent total coagulum refers to all coagulum produced, both filterable and remaining as fouling on the impeller and walls of the reactor. This value is measured by recovering the coagulum by filtration and by scraping from the equipment, drying it, weighing it, and calculating its percent weight based on the calculated solids. Values in excess of 0.75 percent indicate that objectionable kettle fouling would occur in commercial scale batches which would cause serious problems in product yields, product handling and equipment clean-up.

Specific viscosity measurements are made on 1 percent solutions in dimethyl sulfoxide at 25C.

Tensile (P.S.l.) and elongation are measured according to ASTM Method D-882-67 after conditioning at 65 percent and 80 percent relative humidity. The wet values are obtained on 4 mil films which are immersed in water for 5 minutes.

Example 9 uses diethyl maleate as the dialkyl maleate component while all of the other examples use dimethyl maleate. Examples 1, 4, 5 and 7 to 9 use a phosphate ester of an octyl phenol-ethylene oxide condensate (PEOPEO) while the other examples use a phosphate ester of a nonyl phenol-ethylene oxide condensate (PENPEO). Example 1 uses a single surfactant while Examples 2 to use a combination of a major amount of PEOPEO or PENPEO with a minor amount of sodium dihexyl sulfosuccinate (SDS) which is available commercially as AEROSOL M.A. from American Cyanamid. Note in Examples 2 to 10 that when a combination of surfactants is used, the percent total coagulum is significantly lower than in Example 1 wherein a single surfactant is used.

Examples 1 to 4 and 7 to 10 are prepared using ammonium hydroxide as the buffer agent while Examples 5 and 6 use sodium hydroxide. The high wet tensile strength of the polymers prepared in Examples 1 to 5 and 7 to 10 using ammonium hydroxide, indicate their suitability for use as a size in a water jet weaving process.

The polymeric products of Examples 2 and 3 contain only 3.35 percent acrylic acid monomer. These polymers have good water resistance, tensile and elongation making these polymers very suitable for use in water jet weaving processes using organic solvent desizing methods.

In order to be suitable for use as sizes in the water jet weaving process the polymeric size must have a good tensile strength, toughness and adhesion to the yarn under wet conditions. The specific viscosities of the polymers of the present invention are good indices as to wet tensile strength and toughness when considered in the context of the type and amount of comonomers present in the polymer. The preferred polymers of the present invention have a specific viscosity in the range of from 1.2 to 12.0 and more preferably in the range of from 1.3 to 10.0.

The correlation between specific viscosity of the polymers of the present invention and wet tensile strength are shown in the following Table 11 wherein five series of polymers are prepared using the general procedures of Examples 2 to 10 above. Variations in the amount of catalyst and polymerization temperatures lead to variations in the specific viscosity of the resulting polymers. These polymers are then tested for wet tensile strength and the results are tabulated in the following Table 11.

Polymers are prepared using the following by weight monomeric charges A vinyl acetate/dimethyl maleate/acrylic acid 91 .65/5.0/3.35

B vinyl acetate/dimethyl maleate/acrylic acid 90.5 /5 /4.5

C vinyl acetate/dimethyl maleate/acrylic acid 90 I5 /5 D vinyl acetate/diethyl maleate/acrylic acid 90.5 /5 /4.5

E vinyl acetate/dibutyl maleate/acrylic acid 91.65/5 [3.35

Tensile values for C-1 and C-2 are determined at R.ll.

The data in the foregoing Table II illustrate that in a given series, using the prescribed dimethyl maleate and diethyl maleate monomers of the present invention, the greater the specific viscosity the greater is the wet tensile strength. On the other hand, Series E prepared using dibutyl maleate has very low wet tensile strength as compared to comparable polymers having approximately the same specific viscosity. In this regard attention is directed to a comparison between Series E and Series A-3, A-4, B-1 and 13-2.

EXAMPLES 11 to 13 The following Examples 1 1 to 13 are set forth as control examples to illustrate the effect of polymerization temperature on the physical properties of the resulting latex. In each example the general charge and procedure of Example 10 is repeated while the polymerization temperature is varied. The specific viscosity of the resulting polymer is then measured. The results are tabulated in Table 111 below.

TABLE III SUMMARY OF EXAMPLES 11 to 13 Example Polymerization TempfC. Specific Viscosity 1 1 3539 run coagulated 12 46-50 2.12

The data in the foregoing Table 111 indicates that, within the framework of the present invention polymerization temperatures below 40C. lead to coagulation while increasing temperatures above 45C. lead to polymers with decreasing specific viscosities.

However, for any given polymer system within the framework of the present invention, optimum specific viscosity is obtained when the polymerization reaction is in the range of from 40 to 60C. and more preferably from 40 to 50C.

The following Examples 14 to 19 are set forth to further illustrate the criticalities of the present invention.

EXAMPLE 14 The general charge and procedure of Example 3 is repeated here except that fumaric acid is substituted for the acrylic acid used in Example 3. The reactants are mixed and heated. No significant polymerization reaction has taken place even after 24 hours.

EXAMPLE 15 Example l4 is repeated here except using crotonic acid in place of fumaric acid. The polymerization is carried out for 5% hours. At the end of this time, the reaction mixture is found to contain 9 percent by weight of free monomer based on the total latex weight. This low conversion rate makes the polymer process unacceptable for use on a commercial scale. Moreover, the polymer is found to have a specific viscosity of only 1.1 and is unacceptable for use as a size in a water jet weaving process.

EXAMPLE 16 In this example 88 percent by weight of vinyl acetate, 5 percent by weight of dimethyl maleate and 7 percent by weight of monomethyl maleate are interpolymerized according to the general procedure of Example 10.

The monomethyl maleate monomer is being used in place of the acrylic acid used in Example 10. The resulting polymer is found to have a specific viscosity of 1.8, Tensile Strength of 1,880 psi dry and 1,060 psi wet and elongation of 200 percent dry and 500 percent wet. The low wet tensile strength of this polymer coupled with poor wet adhesion to acetate fibers and film insolubility in aqueous alkali, makes it unacceptable for use as a size in a water jet weaving process.

EXAMPLE 17 In this example dibutyl maleate is used in place of the dimethyl maleate and diethyl maleate used in Examples 1 to above. The general polymerization procedures used in Example l are followed here using 91.65 percent by weight of vinyl acetate, 5.0 percent by weight of dibutyl maleate and 3.35 percent by weight of acrylic acid. The resulting polymer has a specific viscosity of 1.79, tensile strength of 2,050 psi dry and 680 psi wet and elongation of 230 percent dry and 240 percent wet. The low wet tensile strength of this polymer makes it unacceptable for use as a size in a water jet weaving process.

EXAMPLE 18 In this example methyl methacrylate is used in place of the dimethyl maleate used in Examples 1 to 8 and 10 above. The general polymerization methods of Example 4 are used here using a monomer charge of 89 percent by weight of vinyl acetate, 5 percent by weight of methyl methacrylate and 6 percent by weight of acrylic acid. The reaction mixture coagulated and no polymer was obtained for testing.

EXAMPLE 19 In this example acrylonitrile is used in place of the dimethyl maleate used in Examples 1 to 8 and 10 above. The general polymerization methods of Example 4 are followed using a monomer charge of percent by weight of vinyl acetate, 5 percent by weight of acrylic acid.

After four hours reaction time only 6.5 percent of the monomers have been converted into polymer.

EXAMPLE 20 This example illustrates the criticality of using a surfactant which is a phosphate ester of an alkyl phenolethylene oxide condensate. Example 4 is repeated here except that octyl phenol-ethylene oxide condensate is used as the surfactant in place of the phosphate ester of octyl phenol-ethylene oxide condensate used in Example 4. The octyl phenol-ethylene oxide condensate used in this example is a well-known surfactant which is available commercially as Triton X-405 from Rohm and Haas. After three hours reaction time the batch was completely coagulated.

EXAMPLE 21 Example 20 is repeated here except using a surfactant which is a phosphate ester of an aliphatic alcoholethylene oxide condensate. After three hours reaction time the batch was completely coagulated.

PART B TESTING OF THE LATICES OF EXAMPLES 1 to 5 AND 7 to 10 AS TEXTILE SIZES and alkaline earth metal hydroxides as well as aqueous solutions of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propyl amine, n-butyl amine, morpholine, etc.

The key properties considered in these tests are listed below:

Solubility all of the latices in question are soluble in aqueous bases such as aqueous ammonium hydroxide to provide sizing solutions.

Sizing Solutions prepared from the latices of Examples l to 5 and 7 to 10 have Brookfield viscosities in the range of from 1 to 300 centipoises at 4 to 5 percent solids allowing ease of application to the yarn.

Wet Tensile Strength films prepared from the latices of the present invention have wet tensile strength in excess of 1,000 psi and the necessary toughness and film integrity required in water jet sizes.

% Elongation these values further indicate that the latices in question have the necessary film toughness required in water jet sizes.

Adhesion the latices of Examples 1 to 5 and 7 to 10 have been tested and found to have good adhesion to the following yarns filaments, acetate, polyester, rayon, texturized polyester, nylon; spun polyester, cotton, rayon and wool; acetate, nylon and blends thereof.

Resolubility in mild alkali dried films of the latices in question are readily soluble in tctrasodium pyrophosphate surfactant solutions which indicates that the size is easily removed from the woven fabric. The size is also soluble in chlorinated solvents used in desizing operations.

Size efficiency is a measure of the amount of size add-on required in a given operation. The add-on is the amount of size that must be applied to the yarn in order to permit it to be woven on a water jet loom. In general, the less size add-on required, the more efficient the size. Sizes prepared from the latices of the present invention have excellent efficiency as is indicated by the following Examples 22 to 24.

EXAMPLE 22 A latex composition is prepared as in Example 10 above using monomeric charge of 90.5 percent by weight of vinyl acetate, 5 percent by weight of dimethyl maleate and 4.5 percent by weight of acrylic acid. The resulting latex, wherein the polymer component has a specific viscosity of 2.7, is dissolved in aqueous ammonium hydroxide to give a 5.0 percent solids solution having a pH of 9.0.

This sizing solution at 120F. is applied to a 150 denier, 41 monofilament, low twist bright acetate yarn on a commercial eleven can slasher at a rate of 90 yards per minute for a size add-on of 2.1 percent. Drying cam temperatures on the slasher are l85/200/200 /215/220/220/230/220/2l0/80/l30F. respectively. The split is very easy, and no ends break out at start-up.

The sized warp is entered into a Nissan Prince water jet loom, where at 400 picks per minute the weaving operation runs at very high efficiency, 98 percent) with no second quality fabric produced. The woven fabric has a dry appearance in contrast to warps woven with lower M.W. (specific viscosity of 0.7) materials which become wet" and slimy. Successive The size is also removable in a chlorinated solvent scouring process.

EXAMPLE 23 Example 22 is repeated here using a latex with a specific viscosity of 2.73. This latex is dissolved with aqueous ammonium hydroxide to give a 4.5 percent solids solution having a pH of 9.2. The size is applied to a 75 denier 20 monofilament low twist (75/20/LT) bright acetate yarn on a seven can slasher. The slasher is run at 25 yards per minute at a size add-on of 1.9 percent using drying can temperatures of 150/170/210 /l60/l90/l50/cold, respectively. The warp splits very easily and weaves at very high efficiency to give good quality fabric which is desized as in Example 22.

EXAMPLE 24 This example is set forth to illustrate the exceptional efficiency of the sizes prepared according to the processes of the present invention. Example 22 is repeated here using a latex with a specific viscosity of 2.73. This latex is dissolved with aqueous ammonium hydroxide to give a 4.5 percent solids solution having a pH of 9.2. The size is applied to a 150 denier, 40 monofilament, 0.8 twist (l/40/0.8) bright acetate yarn on a seven can slasher at yards per minute at a size add-on of 1.6 percent. Drying can temperatures are l/210/210/210/190/cool. The warp splits very easy, and no ends break out during the sizing operation. The warp weaves at very high efficiency to give good quality fabric which is desized as in Example 22. The add-on rate (1.6 percent) used in this example is unusually low when compared to the sizes of the prior art which must be used in much larger amounts.

Sizes which are obtained from polymers prepared by the processes of the present invention are compared to commercially available textile sizes. The results of these comparisons is set forth below. In these tests the toughness value is the product of tensile times elongatron.

Various sizes in the form of ammonium salts are applied to acetate and polyester filaments under water jet conditions. The size is tested for wet tensile, wet elongation, wet toughness and wet adhesion. The results are tabulated in the following Table IV.

Size A is obtained from a latex that is prepared according to the processes of the present invention. Sizes C to G are commercially available sizes which are q TABLE IV.'lESTS ON WATER JET SIZE ON ACETATE AND POLYESTER FILAMENT Percent Tough- Adhesion 2 Specific Tensile elonganess Size Composition 1 viscosity (p.s.i.) tion (X10 Acetate Polyester A VA/DMM/AA 90. 5/5/54. 5 2. 36 2, 540 116 Excellent Good. B VA/DBM/AA 01. 65/5/33. 35 1. 79 700 250 17. 5 Poor Poor. C VA/CA 96/4 0.7 750 200 15 00 Good D VA/MMM 93/7 1. 4 700 400 28 Fair Poor. E VA/MIBM 79/21 1. 9 60 540 3. 2 Good. Do. F VA/MA 47/53 0 0 Poor. Do. G AA/AE 480 200 9.6 Good. Excellent.

1 Values are in weight percent: VA=viny1 acetat monomethyl maleate; M1 BM =monoisobut anhydride; AE=acrylate ester.

2 Qualitative adhesion tests are run under wet conditions on fiber inbedded into size.

warps shows the same excellent performance. This fabric was desized in a conventional process by scouring in tctrasodium pyrophosphate wetting agent baths.

representative of the prior art. Note that Size A has good to excellent adhesion and is at least five times (5X) tougher than the sizes of the prior art.

e; DMM=dimethyl maleate; DBM=dibutyl maleate; MMM= yl maleate; AA=acrylic acid; CA=crotonic acid; MA=ma1eic CONVENTIONAL SIZE N AcsrArsfiKvofi AND TEXTURIZED POLYESTER Various sizes in the form of sodium salts are applied to filament acetate, rayon filament and texturized polyester. The sizes are then tested under conditions of 65% R.H. for tensile, elongation, toughness and adhesion. The results are tabulated in the following Table V.

TABLE V I Compositions A to F are the same as in Table IV above except that A has a specific viscosity of 2.94.

G is a commercial gelatin size.

H is an equimolar styrene maleic anhydride copolymer.

Numerical values are pounds required to break l X A inch lap joints.

Size A, which is obtained from a latex prepared according to the processes of the present invention, exhibits greater toughness and better adhesion than the sizes of the prior art.

LOOM FINISH ACETATE AND NYLON SIZES Various sizes in the form of ammonium salts are applied to acetate and nylon filament yarns. In the acetate application the size remains on the resulting fabric as a 12 TABLE Vi Loom Finish Acetate and Nylon Sizes Size Tensile Elong- Toughness (psi) ation (X 10) Acetate Nylon A 3450 370 I28 19 13 B 2060 230 47 9 I C I660 130 22 27 l l D 225 0 l 36 l4 16 E 3830 20 8 l4 1 l Polyvinyl 2000 500 l00 15 Alcohol Compositions A to E same as in Table IV above except that A has a specific viscosity of 2.66. The polyvinyl alcohol used is a partially hydrolyzed low molecular weight polymer which cannot be used as a loom finish because of its water sensitivity.

Tested as in Table V.

Once again, Size A, which is representative of the sizes of the present invention, shows superior toughness. The. adhesion of this size to acetate and nylon further indicate its utility as a textile size.

, SPUN SIZES FOR AQUEOUS REMOVABLE AND SOLVENT REMOVABLE APPLICATIONS In certain applications it is desirable to size yarns such as cotton, rayon, wool, polyester and blends thereof and thenremove the size from the resulting fabric using either aqueous alkali on an organic solvent. In the following tests various sizes are applied to polyester and then tested under conditions of percent R.H. for tensile, elongation, toughness, adhesion and solubility. The test results are tabulated in the following Table VII.

TABLE VII [Spun sizes for aqueous removable and solvent removable applications] Percent Solubility 3 'Ienslle elon- Tough- Adhesion (p.s.1 gation nessXlO (p.s.i.) Aqueous Organic 3, 500 360 126 180 Yes 1,000 400 40 Yes. 1, 500 200 30 Yes 2, 000 200 40 80 Yrs. 650 620 40 100 Yes N0. 4, 800 420 100 Yes No 6, 600 320 210 40 Yrs 2, 800 60 17 70 Yes. Starch binder" 2 700 30 8 60 Yes No l Compositions A to E same asin Table l\' above (Xttpt of 3.71 and a \A/DVM/AA composition ()[90/5/51 by weight. weight partially hydrolyzed polyvinyl alcohol. PVOli-FII is hydrolyzed polyvinyl alcohol. acrylate binder. Starch/hinder is a blend of starch and an acrylatv 1 Adhesion tests are run on a that A has a specific viscosity l\'() lI-Pll is a high molecular a high molvuilar Weight fully blond oi carhoxyniethyl cellulose and an hinder.

square inch polyester to wood board bond.

CMC/hindcr is a 3 The aqueous solution contains a tetrasodium pyrophosphate-wetting agent combination. The organic solvent used is trlchlorocthylene.

loom finish. Sizes used in this application must be very resistant to water spotting. The sizes are then tested under conditions of 65% RH. for tensile, elongation, toughness and adhesion. The results are tabulated in the following Table VI.

Size A which is representative of the sizes of the present invention exhibits excellent toughness and adhesion. Moreover, this material is removable in conventional aqueous desizing operations as well as in or ganic solvent desizing operations. This latter feature is especially important where water shortages or water pollution problems exist.

Another feature of the present invention is the fact that the polymeric material may be dissolved in organic solvents to form a size. This feature is especially desirable in certain applications wherein solvent size removal techniques are also employed. In such applications the polymer solids are recovered from the latex, using conventional means. The polymer solids are then dissolved in an organic solvent to form the textile size and the size in the form of an organic solvent solution is applied. Size removal may be accomplished using aqueous alkali or organic solvent methods.

Preferred organic solvents used in preparing the sizes are alcohols, ketones, esters and aromatic solvents. Especially preferred are chlorinated aliphatic hydrocarbons such as methylene chloride, methylene bromide, chloroform, bromoform, ethylene dichloride, ethylene dibromide, ethylidene chloride, ethylidene bromide, s-tetrachloroethane, hexachloroethane, s-

dichloroethylene, 1,1 l -trichloroethane, 1,1 ,2- trichloroethane, trim ethylene bromide trichlorobromoethane, trichloromethane, 1,2,3 trichloropropane, 1 l ,2-trichloropropane, trifluorotheir generally lower cost, greater availability and the ease with which these solvents may be handled.

'From the foregoing, it should be obvious that many variations are possible in the present invention without departing from the spirit and scope thereof.

What is claimed is:

1. A process for the preparation of a textile size which comprises:

A. interpolymerizing from 83 to 95 percent by weight of vinyl acetate, from 2 to percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system using a surfactant which is a phosphate ester of an alkyl phenolethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms; and

B. dissolving the resulting latex in a basic aqueous medium to form the textile size.

2. A process as in claim 1 wherein the amount of vinyl acetate is in the range of from 87.5 to 91 percent, the amount of dialkyl maleate is in the range of from 5 to 7.5 percent by weight and the amount of acrylic acid is in the range of from 4 to 6 percent by weight.

3. A process as in claim 1 wherein the dialkyl '4 maleate is dimethyl maleate.

4. A process as in claim 1 wherein the surfactant is a phosphate ester of tertiary octyl phenol-ethylene oxide condensate.

5. A process as in claim 1 wherein the surfactant is a phosphate ester of nonyl phenol-ethylene oxide condensate.

6. A process as in claim 1 wherein the polymerization temperature is in the range of from 40 to 60C.

7. A process for the preparation of a textile size which comprises:

A. interpolymerizing at a temperature in the range of from 40 to 50C. from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system using a surfactant which is a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms; and

8. A process as in claim 7 wherein the surfactant is a phosphate ester of tertiary octyl phenol-ethylene oxide condensate.

9. A process as in claim 7 wherein the surfactant is a phosphate ester of nonyl phenol-ethylene oxide condensate.

10. A process for the preparation of a textile size which comprises:

A. interpolymerizing at a temperature in the range of from 40 to 50C. from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system using a surfactant which is selected from the group consisting of a phosphate ester of nonyl phenol-ethylene oxide condensate and a phosphate ester of tertiary octyl phenol-ethylene oxide cBTiiihsaieTahd f' A Q i B. dissolving the resulting latex m a basic aqueous medium to form the textile size.

11. A process as in claim 1 wherein the basic aqueous medium contains a base selected from the group consisting of alkali hydroxides, alkaline earth hydroxides, ammonium hydroxide, lower mono-, diand trialkylamines and morpholine.

12. A process for the preparation of a textile size which comprises:

A. interpolymerizing from 83 to percent by weight of vinyl acetate, from 2 to 10 percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system containing a phosphate ester of an alkyl phenolethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms and a co-surfactant selected from the group consisting of alkylaryl sulfonated, fatty alcohol sulfates and dialkyl sulfosuccinates,

B. dissolving the resulting latex in an aqueous basic medium to form the textile size.

13. A process as in claim 12 wherein the amount of vinyl acetate is in the range of from 87.5 to 91 percent, the amount of dialkyl maleate is in the range of from 5 to 7.5 percent by weight and the amount of acrylic acid is in the range of from 4 to 6 percent by weight.

14. A process as in claim 12 wherein the polymerization'temperature is in the range of from 40 to 50C.

15. A process for the preparation of a textile size which comprises:

A. preparing an aqueous latex of solids content in the range of 15 to 65 percent by weight by interpolymerizing from 83 to 95 percent by weight of vinyl acetate, from 2 to 10 percent by weight of a dialkyl maleate selected from the group consisting of dim ethyl maleate and diethyl maleate and from h 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers, at a temperature in the range of 40 to 60C., in a latex polymerization system with a surfactant which is a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms, the surfactant comprising between 1 and 4 percent by weight of the total weight of the latex and a co-surfactant selected from the group consisting of alkylaryl sulfonates, fatty alcohol sulfates and dialkyl sulfosuccinates, comprising between 0.1 and 0.3 percent by weight of the total weight of the latex, wherein the resulting inter I polymer has a specific viscosity in the range of 1.2

16. A process as in claim 15, wherein the basic aqueous medium contains a base selected from the group consisting of alkali hydroxides, alkaline earth hydrox ides, ammonium hydroxide, lower mono-, diand trialkylamines, and morpholine.

17. A process as in claim 15, wherein the surfactant is selected from the group consisting of phosphate esters of tertiary octyl phenol-ethylene oxide condensate and nonyl phenolethylene oxide condensate.

i F I t

Claims

1. A process for the preparation of a textile size which comprises: A. interpolymerizing from 83 to 95 percent by weight of vinyl acetate, from 2 to 10 percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system using a surfactant which is a phosphate ester of an alkyl phenolethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms; and B. dissolving the resulting latex in a basic aqueous medium to form the textile size.

3. A process as in claim 1 wherein the dialkyl maleate is dimethyl maleate.

6. A process as in claim 1 wherein the polymerization temperature is in the range of from 40* to 60*C.

7. A process for the preparation of a textile size which comprises: A. Interpolymerizing at a temperature in the range of from 40* to 50*C. from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system using a surfactant which is a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms; and B. dissolving the resulting latex in a basic aqueous medium to form the textile size.

10. A process for the preparation of a textile size which comprises: A. interpolymerizing at a temperature in the range of from 40* to 50*C. from 87.5 to 91 percent by weight of vinyl acetate, from 5 to 7.5 percent by weight of a dimethyl maleate and from 4 to 6 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system using a surfactant which is selected from the group consisting of a phosphate ester of nonyl phenol-ethylene oxide condensate and a phosphate ester of tertiary octyl phenol-ethylene oxide condensate; and B. dissolving the resulting latex in a basic aqueous medium to form the textile size.

11. A process as in claim 1 wherein the basic aqueous medium contains a base selected from the group consisting of alkali hydroxides, alkaline earth hydroxides, ammonium hydroxide, lower mono-, di- and trialkylamines and morpholine.

12. A process for the preparation of a textile size which comprises: A. interpolymerizing from 83 to 95 percent by weIght of vinyl acetate, from 2 to 10 percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers, in a latex polymerization system containing a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms and a co-surfactant selected from the group consisting of alkylaryl sulfonated, fatty alcohol sulfates and dialkyl sulfosuccinates, B. dissolving the resulting latex in an aqueous basic medium to form the textile size.

14. A process as in claim 12 wherein the polymerization temperature is in the range of from 40* to 50*C.

15. A process for the preparation of a textile size which comprises: A. preparing an aqueous latex of solids content in the range of 15 to 65 percent by weight by interpolymerizing from 83 to 95 percent by weight of vinyl acetate, from 2 to 10 percent by weight of a dialkyl maleate selected from the group consisting of dimethyl maleate and diethyl maleate and from 3 to 7 percent by weight of acrylic acid based on the total weight of the monomers, at a temperature in the range of 40* to 60*C., in a latex polymerization system with a surfactant which is a phosphate ester of an alkyl phenol-ethylene oxide condensate wherein the alkyl group contains seven to 11 carbon atoms, the surfactant comprising between 1 and 4 percent by weight of the total weight of the latex and a co-surfactant selected from the group consisting of alkylaryl sulfonates, fatty alcohol sulfates and dialkyl sulfosuccinates, comprising between 0.1 and 0.3 percent by weight of the total weight of the latex, wherein the resulting interpolymer has a specific viscosity in the range of 1.2 to 12.0, B. dissolving the resulting latex in a basic aqueous medium to form the textile size.

16. A process as in claim 15, wherein the basic aqueous medium contains a base selected from the group consisting of alkali hydroxides, alkaline earth hydroxides, ammonium hydroxide, lower mono-, di- and trialkylamines, and morpholine.