MXPA97001751A - Latex thermally sensitized - Google Patents

Latex thermally sensitized

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Publication number
MXPA97001751A
MXPA97001751A MXPA/A/1997/001751A MX9701751A MXPA97001751A MX PA97001751 A MXPA97001751 A MX PA97001751A MX 9701751 A MX9701751 A MX 9701751A MX PA97001751 A MXPA97001751 A MX PA97001751A
Authority
MX
Mexico
Prior art keywords
latex
monomaleate
phm
integer
range
Prior art date
Application number
MXPA/A/1997/001751A
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Spanish (es)
Other versions
MX9701751A (en
Inventor
Rouviere Fabienne
Francine Jeanne Muller Pascale
Original Assignee
The Goodyear Tire&Amprubber Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Goodyear Tire&Amprubber Company filed Critical The Goodyear Tire&Amprubber Company
Publication of MX9701751A publication Critical patent/MX9701751A/en
Publication of MXPA97001751A publication Critical patent/MXPA97001751A/en

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Abstract

The present invention relates to a process for preparing a thermally sensitizable latex which is characterized by the steps of (1) polymerizing at least one conjugated diolefin monomer in an aqueous polymerization medium by free radical polymerization in the presence of an emulsifier system which it is comprised of a fatty ethoxylated monomaleate and optionally an alkyl monomaleate to produce a first latex composition, and (2) adding a water soluble organically modified polysiloxane to the first latex composition to produce the thermally sensitized latex.

Description

LATEX THERMALLY SENS I B I L I ZABLE BACKGROUND OF THE INVENTION Latex is commonly used as a chemical binder for non-woven fabrics to provide non-gejid fabric with desired physical characteristics, such as increased resistance. The non-woven fabric is usually immersed in the latex to saturate it with the latex. If the non-woven fabric has a thickness of less than about 3 mm (millimeters), it can simply be dried to remove the water from the latex; This leaves the latex polymer dispersed through the non-woven fabric. However, in cases where the non-woven fabric is thicker than about 3 mm, the water in the latex tends to get trapped inside the non-woven fabric. To overcome this problem, thermal sensitization of latex is commonly used as the chemical agglutinant for non-woven fabrics that are thicker than approximately 3 mm. After being saturated with thermally sensitive latex, the non-woven fabrics can be heated above the latex coagulation temperature to induce coagulation. After the coagulation occurs, the water can be squeezed out of the non-woven fabric which eliminates the problem of water getting trapped inside the non-woven fabric. The rubbery polymer q disperses through the non-woven fabric, then, of course, can be cured to achieve the desired physical characteristics.
The use of thermally sensitive latexes as chemical binders for non-woven fabrics is well known. For example, U.S. Patent 4,001,162 and U.S. Patent 4,535,111 disclose that thermally sensitized latex mixtures can be used to impregnate nonwoven material and to produce hollow bodies, e.g., gloves, by the dipping process. U.S. Patent 4,535,111 also teaches that organically modified water-soluble loxanes, such as polyalcoxane oxides, can act as heat sensitizing agents. Additionally, numerous publications describe other thermal sensitizing agents, such as pol i v ini 1 alkyl ethers, polyacetale active substances with cation, polyetheramines and polyethylene oxides. US Pat. No. 4,250,071 discloses that ammonia and polyalkazole alkoxylates can be used as thermal sensitizers for rubber latexes and that the thermally detectable lipids obtained in this way are stable so that coagulation does not occur. even in case of prolognado storage or under mechanical effort. The thermostatic thermally stable latex 1 is usually synthesized by using one or more diolefin monomers, which comprise at least one carboxyl group containing onerous, and optionally additional monomers which are copolysable with the same in an emulsion containing both an anionic emulsifier as a non-ionic emulsifier. Accordingly, these thermally sensitive latices generally contain both an anionic emulsifier and a nonionic emulsifier, as well as rubbery polymer containing a monomer containing carboxy group 1 or.
SUMMARY OF THE INVENTION Using the techniques of this invention, the latices which are capable of becoming thermally stable can be synthesized without including a monomer containing carboxy group in the monomer charge composition. Consequently, the need to incorporate a monomer containing carboxyl group in the rubbery latex polymer is undermined. The need to include both an anionic emulsifier and a nonionic emulsifier in the polymerization medium is also eliminated. This invention more specifically discloses a process for preparing a thermostable thermally available latex comprising the steps of (1) polymerizing at least one conjugated diole monomer in an aqueous polymerization medium by free radical polymerization, in the presence of a emulsifying system which is comprised of a fatty ethoxylated monomaleate and, optionally, an alkyl monomaleate to produce a first latex composition; and (2) adding a modified water soluble organic polysiloxane to the first lathe composition to produce a thermally sensitive latex 1izable. The present invention also discloses a latex that can be made thermally stable, which is comprised of (1) at least one rubbery polymer, (2) water and (3) an emulsifier system that is comprised of an ethoxylated monomaleate g and optionally an alkyl monomaleate. The present invention further discloses a thermally reachable thermal latex composition which is comprised of (1 at least one rubbery polymer, (2) aGUA, 93) an emulsifier system which is comprised of ethoxylated monomaleate, and optionally an alkyl monomaleate and (4) at least one organically modified polysiloxane, soluble in water.
Detailed Description of the Invention The latices of this invention are made by a free radical emulsion polymerization process. In the process used, at least one conjugated diolefin monomer is polymerized in an aqueous polymerization medium. It is also possible to copy the conjugated diolefin monomer with additional monomers which are copolymers which can be admixed therewith, such as vinyl aromatic monomers, acrylonitrile monomers or allylpropeneic acid ester monomers. The conjugated diolefin monomer will normally contain from 4 to about 8 carbon atoms with 1,3-butadiene and isoprene being typical examples Virtually any vinyl aromatic monomer known to polymerize in free radical systems can be polymerized with the conjugated diolefin monomers. These aromatic vinyl numbers typically contain from 8 to 20 carbon atoms. Usually, the aromatic vinyl monomer will have from 8 to 14 carbon atoms. Some representative examples of vinyl aromatic monomers that can be used include styrene, 1-v ini-1-naphthalene, 2-vinyl naphthalene, 3-methyl e-tyne, 4-propyl styrene-t-butyl styrene, 4-cyclohexyl styrene 4- dodecyl styrene, 2-et i 1 -4-benzyl 1 styrene, 4- (phenyl lbutyl 1) is reindeer and the like. Styrene is generally the most preferred vinyl aromatic monomer. The allylpropenoic acid ester monomers can also be copolymerized with the conjugated diolefin monomers to produce the latex. The monomers of acid ester to the quinolone that can be used generally have structural form 1: R '0 CH2 = C-C-O-R wherein R represents an alkyl group containing from 1 to 10 mos of carbon with n being an integer from 1 to 8) and wherein R 1 represents a hydrogen atom or a methyl group (R '= C H ", with n being 0 or 1). In the cases where R1 is a n 2n + 1 methyl group, the alkyl propenoic acid ester monomer can be described more fully as a monomer of alkyl ethacrylate. The methylated methacrylate and ethanolamine, propylmethacrylate and n-butymetacrite are representative examples of alkylmetharylate groups that could be used. The alkyl group in the preferred alkyl propenoic acid ester monomer will contain from 1 to 4 carbon atoms with the alkyl groups containing 4 carbon atoms being most preferred. Consequently, the most preferred alkyl monomers, with the 1-acrylate, 1-acrylate and 1-acrylate, are the most preferred alkyl ester of propene ester, with the i 1 ato being the most preferred. The alkyl groups in said alkyl propenoic acid ester monomers may be straight or branched chain. Thus, normal propyl acrylate, iso propyl acrylate, normal butyl acrylate or tertiary butyl acrylate can be used. Normal butyl acrylate is a particularly preferred monomer. The first step of the polymerization process is carried out by adding the appropriate monomers and a very specific emulsion system to water in order to form an aqueous polymerization medium. The polymerization of the monomers is then initiated with a free radical generator. The ratio between the total amount of monomerspressed in the charge composition and water may vary between about 0.2:: 1 and about 1.2: 1. It is generally preferred that the ratio of monomers including alkyl monomaleate to water in the filler composition be within the alder scale of 0.8: 1 and approximately 1.1: 1. For example, it is usually very satisfactory to use a ratio of monomers that are not dependent on water in the charge composition that is within the range of 0.8: 1 to about 1: 1. The aqueous polymerization medium will also contain an emulsifier system which is comprised of a monomaleate of the fatty side and optionally an alkyl monomaleate. The fatty acid ethoxylated monovates that can be used will normally be of the structural formula: 0 H0 0C-CH = CH-C-0 - (- CH2-CH2-0 - ^ - (CH2 -) - CH3 where x represents an integer from 1 to approximately 30 and where y represents an integer from 5 to approximately 20. It is usually preferred that x represent an integer from 2 to 20 and stop and represent an integer from 8 to 16. Generally it is more preferred that x represent an integer from 3 to 8 and that y represent an en ro from 10 to 12. The alkyl monomaleates that can be used normally will be of the structural formula: 0 H 00C-CH = CH-C-0 (-CH2 -) ^ CH3 where n represents an integer from 0 to 7. Normally it is prefixed that n represent an integer from 1 to 4 with 1 or 2 being more preferred. The most preferred one for n is to represent 1. The fatty ethoxylated monomaleate will normally be added to the aqueous polymerization medium in an amount ranging from about 0.5 to about 6 phm (part by weight per 100 parts by weight of monomers including alkyl monomale). In this way, it will typically be present in the latex in an amount that is within the range of about 0.5 to about 6 phdl (parts by weight per 100 parts by weight of dry latex). It is usually preferred that the fatty ethoxylated maletate is present in an amount which is within the range of about 1 phm to about 4 phm. Generally, it is more preferred that the fatty ethoxylated monomaleate be present in an amount that is within the range of about 2 phm to about 3 phm. The alkyl monomaleate will normally be added to the aqueous polymerization medium in an amount that is within the range of about 0 to about 8 phm. It is usually preferred that the alkyl monomaleate be present in an amount which is within the range of about 1 phm to about 5 phm. It is generally more preferred that the alkyl moiety is present in an amount within the range of about 3 phm to about 4 phm. The precise amount of emulsifier system required in order to achieve optimal results will, of course, vary with the polymer being synthesized, with the polymerization conditions, and with the specific emulsification that is being used. For example, the polymerization reaction rate increases with higher levels of fatty ethoxylated monomaleate. Accordingly, lower reaction temperatures with increasing levels of fatty ethoxylated monomaleate will be used. In any case, people experienced in the field can easily assure the specific amount of emulsifier required in order to achieve optimal results. Essentially any type of radical generator can be used to initiate free radical emulsion polymerization. For example, chemical compounds generating free radical, ultraviolet light or radiation can be used. In order to ensure a satisfactory polymerization regime, uniformity and a controllable polymerization, radical generating chemical agents are generally used with good results. Some representative examples of free-lime initiators that are commonly used include the various peroxygen compounds such as potassium persulfate, ammonium persulphite, benzoyl peroxide, hydrogen peroxide, di-t-butyl peroxide, peroxide. of dicuyl, 2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, hydroperoxide of eumeno, p-menthane hydroperoxide, t-buoperoxyperoxide, acetone, acetone, peroxide, dicetyl, t-butyl peroxyacetate, t-butylperoxoleic acid, t-butyl peroxy-zoate, acetyl cyclohexyl-1-sulfonyl peroxide, and the like; the various azo compounds such as 2-t-but-azo-2-cyanopropane, azod ii sobutyrate dimethyl, azod ii sobutyronitrile, 2-t-butylazo-1-cyanocyclohexane, 1-t-amylazo-1-cyanocyclohexane, and the like; and the various alkaline percetals, such as 2, 2-bi s- (t-but i 1 perox i) butane, 3, 3-bi s (t-but i 1 per xi) ethyl butyrate, 1, 1 -di - (-bu lperox i) c ichexano and the others. Persulfate initiators, such as potassium persulfate and ammonium persulfate are especially useful in aqueous emulsion dispersions. The amount of initiator employed will vary with the monomers that are being polymerized and with the desired molecular weight of the polymer being synthesized. Higher molecular weights are achieved by using smaller amounts of the initiator and lower molecular weights are achieved by using larger amounts of the initiator. However, as a general rule, from 0.005 to 1 phm (parts per cent by 100 parts by weight monomer) of the initiator will be included in the reaction mixture. In the case of metal persulfate, the initials will be used more commonly from 0.1 to 0.5 phm in the polymerization medium. The free radical emulsion polymerization will typically be carried out at a temperature that is within the range of about 5QC to about 70QC. It is usually more typical for polymerization to be carried out at a temperature which is within the range of about 15 ° C to about 55 ° C. The polymerization step is allowed to continue until a very high conversion of monomers to polymer is achieved. Typically, the conversion achieved will be in excess of about 96 percent. More typically, monomer conversions in excess of about 98 percent will be achieved, with a quantitative conversion in excess of 99 percent being preferred. The solids content that is normally reached will be on the scale of about 35 percent to about 55 percent. It is usually preferred that the latex have a solids content that is within the range of about 4 percent to about 50 percent. However, the tex will normally be diluted with additional water after the polymerization but before it is used in an application as a thermally sensitive thermal tex. The thermally insensitive latex will normally be diluted to a solids content that is within the range of about 5 to about 40 percent. The latex is made thermally stable by adding at least one organically modified polysiloxane soluble in water to the latex. Said water-soluble organically modified polymers are commercially available from a variety of sources. For example, Hansa Textilchemie sells an organically water soluble polysiloxane like Hansa (R) ' Coagul ant 4710. The organically modified water soluble polysiloxane will typically be added in an amount that is within the range of about 0.1 to 1 phdl (parts by weight per 100 parts by weight of dry latex). The organically soluble polysiloxane soluble in water will typically be added to the latex in a quantity that is within the range of about 0.2 to 0.5 phdl. Generally, the coagulation temperature of the thermically sensitive latex decreases with increasing amounts of polysiloxane. The coagulation temperature of the latex also decreases with increasing levels of solids contents. Various compositional ingredients other than thermally sensitive latex 1 may also be added typically to provide the non-woven fabric being treated with the desired physical properties. For example, fillers, tackifiers, curative pigments and accelerators will typically be added to the thermically sensi bi-free latex. It can then be used as the chemical binder for virtually any type of fabric. woven natural or synthetic. For example, it can be used to treat non-woven fabrics which are comprised of polypropylene, polyethylene, cotton, wool or polyester and the like. This invention is illustrated by the following examples which are merely for the purpose of illustration and should not be construed as limiting the scope of the invention or the manner in which it can be practiced. Unless specifically indicated otherwise, all parts and percentages are given by weight Example 1 A grade ethoxylated monomaleate (B r i j 30 monomaleate) was synthesized by mixing 39.4 g of fatty ethoxylated alcohol having the structural formula CH 3 -CH 2) - (- 0-CH 2 -CH 2 -) - ^ - 0 H with 10.7 g. of maleic anhydride in a glass flask under gentle stirring and holding the flask at a temperature of 50 ° C overnight. An alkyl monomaleate (ethyl monomaleate) was also synthesized by mixing 21.1 g of ethanol with 45 g of maleic anhydride in a glass flask under gentle stirring and holding the flask at a temperature of 50 ° C overnight. Then a latex was synthesized using the techniques of this invention. In the procedure used, an aqueous phase was prepared by heating 1677 g of water at a temperature of 60 ° C and then adding 48 g of Brij30 monomaleate, 64 g of ethyl monomaleate, and 4.8 g of naphthalene sulfonate (a dispersion). The mixture was stirred and its pH adjusted to be within the range of 10 to 11 by the addition of potassium hydroxide. The stirring was continued until the solution became clear and had a very low viscosity. It was then charged to a 5-liter stainless steel reactor and cooled to a temperature of 35 ° C. Then, 576 g of acrylonitrile and 4.8 g of tridodecyl mercaptan were charged to the reactor. This was followed by the loading of 96 g of a 5 percent solution of triethanolamine into the reactor. After the triethanolamine was charged to the reactor, a vacuum was applied and 960 g of 1,3-butadiene were charged to the reactor. The reactor was equipped with three paddles to shake its contents that were operated at a speed of 400 rpm. After about 15 minutes of mixing at a temperature of 355C, the polymerization was initiated by injecting 160 g of a 5 percent solution of potassium persulfate into the reactor. The polymerization was allowed to continue for a period of about 8 hours after which the made latex was discharged from the reactor. The residual 1,3-butadiene monomer was separated from latex by stirring in a flask under suction for several hours. It was determined that the latex has a solids content of 46 percent, a pH of 7.4, a surface tension of 46 mN / m, a Brookfield viscosity (spindle # 1 at 60 rpm) of 25 mPa'se and a particle size at 140 nm. The nitrile rubber in the latex was determined to have a glass transition temperature of -229C. Then a thermically sensitized latex was made 1 sizable I clado 434 g of latex with 1.5 g of sodium sulfonate paraffin 1.5 g of alcohol ethoxylated fatty, 25 g of a 40 percent dispersion of zinc oxide (ZnO), and 0.2 g of polysiloxane (R) Hansa 'Coagulant 4710. Then water was added to adjust the latex to a final solids content of 30 percent with the latex being mixed for 1 hour in a 1 liter beaker equipped with a magnetic stirrer. Then, 15 g of the thermically sensitive thermal latex 1 was added to a 25 ml beaker that was placed in a bath that was maintained at a temperature of 60 ° C. The temperature at which the thermally sensible latex coagulated was observed and then recorded as 43 ° C. In another experiment, the amount of polysiloxane (R) Hansa Coagulant 4710 was increased to a level of 0.3 g. In this experiment, thermally reachable sens i bi 1 latex was coagulated at a temperature of 36 ° C.
Comparative Example 2 The polymerization procedure used in Example 1 was repeated in this experiment, except for the fact that only 3 phm of oct i lmonoma leato and no monornite of Brij 30 were used in the emulsifier system. However, in this experiment, a very low conversion of only about 52 percent resulted. It should be noted that in Example 1, the emulsifier system contained 3 phm of Br i j monomaleate 30 and 4 phm of ethyl monomaleate.
Comparative Example 3 The polymerization procedure used in Example 1 was repeated in this experiment, except for the fact that 4 phm of octylmonomaleate and 5 phm of acetoacetoxim nomaleate are used as the emulsifier system. In this experiment, overheating occurred and the latex was not evaluated.
COMPARATIVE EXAMPLE 4 The polymerization process used in Example 3 was repeated in this experiment, except for the fact that the level of oct i lmonoma leato was decreased to 3 phm. The red acid level of octi lmonoma leato decreased the polymerization rate that maintained the polymerization without overheating. However, the latex made was not thermally sensi bizable without the subsequent addition of a large amount of both nonionic and anionic emulsifiers. Although certain representative embodiments and details have been shown for the purpose of illustrating the present invention, it will be apparent to those experienced in this field that various changes and modifications may be made therein without abrogating the scope of the present invention.

Claims (10)

1. - A process for preparing a thermally slateizable latex characterized by the steps of (1) polyearizing at least one conjugated diolefin monomer in an aqueous polymerization medium by free radical polymerization in the presence of an emulsifying system which is comprised of a fatty ethoxylated monomaleate and optionally a chyle monomaleate to produce a first latex composition; and (2) administering an organically modified water-soluble polysiloxane to the first latex composition to produce thermal latex me sens ibi 1 izabl e.
2. A latex that can be made thermally insurable, characterized in that it is comprised of (1) at least one rubbery polymer, (2) water, and 3) an emulsifying system comprised of a fatty ethoxylated monomaleate. and optionally an alkyl monomaleate.
3. A thermally sensitizable latex composition characterized in that it comprises (1) when a rubbery polymer, (2) water, (3) an emulsifying system that is comprised of a fatty ethoxylated monomaleate and optionally a alkyl monomaleate and (4) at least one non-organically modified water soluble polysiloxa.
4. A latex as specified in the claim characterized in that the rubbery polymer is a nitrile rubber; wherein the fatty detoxylated monomaleate is present in the latex in an amount which is within the range of 0.5 phm to phm; wherein the alkyl monomaleate is present in the latex in an amount that is within the range of 0 to 8 phm; where the latex has a solids content that is within the range of 35 percent to 55 percent.
5. A latex as specified in the claim characterized in that the fatty ethoxylated monomaleate is of the structure for structure 1: H00 C-CH = CH-C-0 (-CH-CH -0-h- (CH0 -) - ^ CH. where x represents an integer from 1 to 30 and where y represents an integer from 5 to 20; wherein the alkyl monomaleate is from the formula 1 to structure 1: H 00 C - C H = C H - C - 0 f C H 2 H - n &H 3 - wherein n represents an integer from 0 to 4; wherein the monomalea to fatty ethoxylate is present in an amount that is within the range of 1 phm to 4 phm; and wherein the chyle monomaleate is present in an amount that is within the range of 1 phm to 5 phm.
6. A latex as specified in claim characterized in that the fatty ethoxylated monomaleate is from the structural form. H00C-CH = CH-C-0 (-CH2-CH2-0 -) - (CH2- -CH3 where x represents an integer from 2 to 20 and where y represents an integer from 8 to 16; wherein the alkyl monomaleate is of the formula structure 1: where n represents an integer from 1 to 2; wherein the monomalea to fatty ethoxylate is present in an amount that is within the range of 2 phm to 3 phm; and wherein the chyle monomaleate is present in an amount that is within the range of 3 phm to 4 phm.
7. A latex as specified in claim characterized in that the fatty ethoxylated monomaleate is of the structural formula: H 00C-CH = CH-C-0-r-CH2-CH2-0 -) - ^ - (CH2) -CH3 where x represents an integer from 3 to 8 and where y represents an integer from 10 to 12; wherein the alkyl monomaleate is of the structural formula: wherein n represents the integer 1; and where the latex has a solids content that is within the range of 40 percent to 50 percent.
8. A thermally sensitive latex as can be specified in claim 3, characterized in that 0.1 phdl to 1 phdl of the organically modified polysiloxane is present in water; where the fatty ethoxylated monomaleate is of the structural formula: H00 C-CH = CK-C- (-CH. • CH2-0 -h 'C4.-) CH and where x represents an integer from 1 to 30 v where y represents an integer of 5 23; wherein the alkyl ronomaleate is structurally 1 to 1: HOOC-C- ^ C -C- C CH 7-r ^ - H3 where n represents an integer from 0 to +; where the monomalea to eto * i I? creso is present in a quantity that is within the range of 1 hm to 4 phm; and where the monopoly of?. qu is present in a? c to 11 d? That is within the range of 1 phm to 5 ohm; wherein the polymethyl or rubbery is a nitrile rubber; and where the thermally sensible latex has a solids content that is within the range of 5 percent to &C percent.
9. A thermally sensitive latex as specified in claim 8, characterized in that the fatty acid monoether is present in an amount that is within the range of 2 phm to 3 phm; wherein the alkyl monomaleate is present in an amount which is within the range of 3 phm to 4 phm; where the monomaleate is made of the structural formula: H00C-CH = CH-C-0- -CH ¿-CH ¿-0-) x (CH ¿-) - yCH or ~ where x represents an integer from 3 to 3 and where y represents an integer from 10 to 12; and wherein the alkyl monmaleate is of the structural formula: H00C-CH = CH-C-C i-CH «¿-) - n CHo" where n represents the integer 1; and wherein thermal sensory bi-viscosity latex is comprised in addition to a filler, a c rature and an accelerator.
10. A process as specified in claim 1, wherein the polymerization is carried out at a temperature which is within the range of 5 Q C to 70 Q C; wherein the ratio between the total amount of monomers present in the charge composition and water is within the range between 0.2: 1 and 1.2: 1; wherein the emulsifying system consists only of the fatty ethoxylated monomaleate and the alkyl monomaleate.
MXPA/A/1997/001751A 1996-03-11 1997-03-07 Latex thermally sensitized MXPA97001751A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US1316496P 1996-03-11 1996-03-11
US013164 1996-03-11
US013,164 1996-03-11

Publications (2)

Publication Number Publication Date
MX9701751A MX9701751A (en) 1997-09-30
MXPA97001751A true MXPA97001751A (en) 1998-07-03

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