Supercritical fluid pressure sensitive adhesive polymers and their preparation

Abstract

Pressure sensitive adhesive (PSA) polymers, especially low Tg, high tack, nonpolar and polar polymers useful in formulating PSA can be solubilized or dispersed in a supercritical fluid (SCF), such as liquid CO2 or supercritical CO2, using an organic cosolvent such as toluene. PSA polymers can be polymerized in SCF fluids to make unique adhesive products. Inclusion of a fluorinated reactant in the SCF polymerization process yields a PSA with improved resistance to mineral oil.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] None

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

[0002] Not applicable.

BACKGROUND OF THE INVENTION

[0003] The present invention relates to the preparation of pressure sensitive adhesive (“PSA”) polymers and more particularly to their preparation in supercritical fluid (“SCF”) reactive medium.

[0004] A variety of coatings have been developed as a response to customer and government demands that volatile organic compounds (“VOCs”) be reduced and/or eliminated from coatings formulations. These include, inter alia, powder coatings, water-borne coatings, high solids organic solvent coatings, and SCF coatings. The use of supercritical fluids as carriers and viscosity reducers for transporting a variety of coating materials and effectively spraying them onto a coatable surface while reducing the amount of VOCs that are required for application has been proposed in a number prior publications. A good review of these publications can be found in, for example, U.S. Pat. No. 5,212,229. Performance reports on SCF coatings can be found, for example, in Goad, et al., “Supercritical Fluid (SCF) Application of SMC Primers: Balancing Transfer Efficiency and Appearance”, SPI Compos Inst Annu Conf Expo, Proc J Soc Plast Ind, vol. 5, 2nd page, Session 21A (1997); and Nielsen, et al., “Supercritical Fluid Coating: Technical Development of a New Pollution Prevention Technology”, Water-Borne & Higher-Solids, and Powder Coatings Symposiun, Feb. 24-26, 1993 New Orleans, LA, sponsored by The University of Southern Mississippi Department of Polymer Science and Southern Society for Coatings Technology.

[0005] Use of SCF technology in the adhesives field, however, has been given little consideration by the art. The present invention, then, is addressed to implementing SCF technology for PSA adhesives.

BRIEF SUMMARY OF THE INVENTION

[0006] One aspect of the present invention relates to stabilizing or dispersing pressure sensitive adhesive (PSA) polymers, especially low Tg, high tack, nonpolar and polar polymers useful in formulating PSAs, in a supercritical fluid (SCF), such as liquid CO2 or supercritical CO2, by using an organic cosolvent such as toluene. Another aspect of the present invention reveals that PSA polymers can be polymerized in SCF fluids to make unique adhesive products. Inclusion of a fluorinated reactant in the SCF polymerization process yields a PSA with improved resistance to mineral oil.

[0007] In this application the term (co)polymer means either a polymer or copolymer, which includes a homopolymer. The term (co)polymerization means either polymerization or copolymerization, which includes homopolymerization. Further, the term (meth)acrylate means either acrylate or methacrylate.

DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention extends the use of fluid CO2 or supercritical CO2 to PSA adhesive systems from its use in coatings systems as proposed in the art. The present invention is based upon several fundamental discoveries with respect to PSA systems and fluid CO2 or supercritical CO2. Initially, certain classes of cosolvents are required in order to stabilize conventional PSA (co)polymers in fluid CO2 or supercritical CO2. Next, it was discovered that PSA (co)polymers could be synthesized in fluid CO2 or supercritical CO2 as the reaction solvent, even to the exclusion of other conventional organic solvents. Further, it was discovered that improved oil and fuel resistance could be imparted to PSA polymers synthesized in fluid CO2 or supercritical CO2 by including a fluorinated monomer in the reaction mixture.

[0009] Referring initially to the use of certain classes of cosolvents to stabilize conventional PSA polymers in fluid CO2 or supercritical CO2, different classes of cosolvents will be required to polar (e.g., acrylics) than for nonpolar (e.g., polybutene) PSAs. For ester type cosolvents for dissolving or dispersing polybutene (typical nonpolar PSA polymer) in fluid CO2 or supercritical CO2, the cosolvent should possess the following characteristics: molecular weight range of 116-297, density range of 0.855-0.898, and χo factor (oxygen heteroatoms) of 0.108-0.275. For alcohol type cosolvents, the cosolvent should possess the following characteristics: molecular weight range of 144-186, density range of 0.827-0.831, and χo factor (oxygen heteroatoms) of 0.086-0.111. Finally, for hydrocarbon type cosolvents, the cosolvent should possess the following characteristics: molecular weight range of 86-227, density range of 0.659-0.865, and χo factor (oxygen heteroatoms) of 0.

[0010] The χ (chi) factor is based upon the McGinniss predictive relationship as defined in Organic coatings in Plastic Chemistry, Vols. 39 and 46, pp. 529-543 and 214-223, respectively (1978 and 1982, respectively). The McGinniss predictive relationship defines the χ factor as a weight fraction of heteroatoms contained in the monomer or in the monomer repeat unit of an oligomer or polymer.

[0011] In adjudging suitable cosolvents, polybutene (MW range of 66,000 to 107,000) was dissolved in fluid CO2 or supercritical CO2 in equal weight parts with the cosolvent and the number of milliliters of CO2 that can be added to a one gram same of the mixture and still remain a clear solution or form a stable dispersion recorded (Solubility Number). Representative such cosolvents, then, are displayed below.

	Cosolvent	χ	Solubility
No.	Type	MW	Density	Factor	Number
1	Trans-2-hexenyl acetate	142.20	0.898	0.225	2.24
2	Ethyl trans-3-hexenoate	142.20	0.896	0.225	2.37
3	Methyl caproate	130.19	0.885	0.246	2.86
4	Isobutyl isobutyrate	144.21	0.855	0.222	2.92
5	Butyl acetate	116.16	0.862	0.275	3
6	Butyl methacrylate	142.20	0.894	0.225	3.52
7	Hexyl acetate	144.21	0.876	0.222	4.32
8	Butyl butyrate	144.22	0.871	0.222	4.36
9	Pentyl Propionate	144.21	0.873	0.222	4.45
10	Methyl ethanoate	144.22	0.870	0.222	4.53
11	Ethyl caproate	144.21	0.873	0.222	4.66
12	Methyl dodecanoate	186.30	0.873	0.172	4.82
13	2-Ethylbutyl acetate	144.21	0.876	0.222	4.91
14	Methyl oleate	296.50	0.867	0.108	5.4
15	Dodecyl acetate	228.38	0.865	0.140	6.39
16	Methyl tridecanoate	228.38	0.864	0.140	6.42
17	Soybean oil methyl esters	250	0.875	0.128	8.48
18	Hexane	86.16	0.659	0	3.93
19	Heptane	100.21	0.684	0	4.26
20	Tetradecane	198.40	0.763	0	4.76
21	Hexadecane	226.45	0.773	0	5.07
22	Toluene	92.14	0.865	0	5.24
24	1-Hexadecene	224.42	0.783	0	6.63
25	1-Dodecanol	186.34	0.831	0.086	2.88
26	1-Nonanol	144.26	0.827	0.111	5.86

[0012] Cosolvents 1-17 are esters, cosolvents 18-24 are hydrocarbons. and cosolvents 25 and 26 are alcohols. The weight ratio of (co)polymer to solvent can vary from, say, about 0.5 to 2.

[0013] One of the major uses or PSAs is to adhere trim and decals on a variety of transportation vehicles (automobiles, buses, trains, tractors, trucks, boats, etc.). Current PSA technology typically uses acrylic based (co)polymers which have excellent adhesion to a variety of polar (painted, non-painted, and active) surfaces. The major problem with current acrylic PSAs is their poor resistance to oils, fuels, and greases commonly found around transportation applications and environments. One aspect of the present invention is the use of special fluorine containing monomers that greatly enhance the oil and fuel resistance of the acrylic PSA, while still maintaining it tack and good adhesive bonding properties.

[0014] By using liquid CO2 or in supercritical CO2 fluids as the polymerization vehicle or media, new (co)polymers can be made from low Tg acrylic monomers in combination with fluorinated (meth)acrylic monomers. Representative low Tg acrylic monomers are ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and dodecyl acrylate. Representative fluorinated (meth)acrylic monomers include trifluoromethylacrylate and trifluoromethylmethacrylate. As the examples will demonstrate that tack values can be formulated to range from between about 480 to 0 by varying the amount of butyl acrylate and fluorinated octylmethacrylate. Resistance to mineral oil, however, can range on up to 30 minutes. An additional advantage of using liquid CO2 or in supercritical CO2 fluids as the (co)polymerization vehicle is that no additional organic solvents are required and the fluorinated monomers assist in stabilizing the PSA (co)polymer product.

[0015] Referring now to suitable polymerizable monomers, broadly, such monomers include any ethylenically unsaturated monomer or oligomer which can be (co)polymerized in the presence of a the initiator. In adhesives technology, acrylic or acrylate compounds find wide acceptance in industry. Another suitable class of ethylenically unsaturated compounds is vinyl compounds, while a third broad class are compounds containing backbone ethylenic unsaturation as typified by ethylenically unsaturated polyester oligomers.

[0016] Referring with more particularity to reactive acrylic or acrylate monomers or oligomers, a variety of monoacrylate monomers find use in accordance with the present invention. Monoacrylates include, for example, allyl (meth)acrylate, C1-C12 alkyl and cycloalkyl (meth)acrylates, such as, for example, butyl acrylate, 2-ethylhexyl acrylate, isooctylacrylate, amyl acrylate, lauryl acrylate, iso-propyl acrylate, and the like, and corresponding monomethacrylates which include, for example, benzyl methacrylate, stearyl methacrylate, decyl methacrylate, cyclohexyl metliacrylate, and the like, and mixtures thereof. The foregoing monomers are merely representative and not limitative of the list of acrylate and methacrylate monomers suitable for use in the present invention as those skilled in the art will appreciate.

[0017] (Co)polymerization conditions comprehend the use of initiator systems appropriate for the (co)monomers involved in the reaction scheme in kind and amount as taught in the arts Temperatures also conventional, although employment of reaction temperatures as low as room temperature can be practiced on occasion due to the use of liquid CO2 or in supercritical CO2 fluids as the reaction media. Pressures, of course, are appropriate for creating liquid CO2 or in supercritical CO2 fluids, again as known in the art.

[0018] In this application, all units are in the metric system unless otherwise expressly indicated. Also, all citations are expressly incorporated herein by reference.

EXAMPLES

Example I

[0019] It is well known that polymers (especially low Tg, high tack, nonpolar and polar polymers) used in PSAs are not soluble or dispersible in liquid CO2 or in supercritical CO2 fluids. Use of certain cosolvents that possess the correct molecular weight, density, and χ factor, however, can be used to dissolve or disperse PSA polymers in liquid or supercritical CO2 fluids. In order to demonstrate this aspect of the present invention, PSA polymers were mixed at a 1:1 weight ratio in either liquid CO2 or in supercritical CO2 with and without the addition of toluene solvent. The following results were recorded.

TABLE I
		Supercritical		Solution or
PSA Polymer*	Liquid CO2	CO2	Cosolvent	Dispersion
Polybutene	Yes	Yes	No	No
Polyisobutylene	Yes	Yes	No	No
Natural Rubber	Yes	Yes	No	No
Polybutylacrylate	Yes	Yes	No	No
Polybutene	Yes	Yes	Yes	Yes
Polyisobutylene	Yes	Yes	Yes	Yes
Natural Rubber	Yes	Yes	Yes	Yes
Polybutylacrylate	Yes	Yes	Yes	Yes
Silicones	Yes	No	No	Partial
Silicones	No	Yes	No	No
Silicones	Yes	Yes	Yes	Yes
*Polybutene: MW 3,000; Polyisobutylene: MW 85,000, Natural Rubber: MW 1,000,000, Polybutylacrylate: MW 700,000

[0020] These results demonstrate that a cosolvent must be used in order to obtain a practical dispersion or solution of the PSA polymer.

[0021] Specific examples of commercial PSA polymers in cosolvents that are soluble in CO2 are displayed in Table II, below.

TABLE II
	Polymer PSA	Molecular	Wt-% in
Sample	Type	Weight	Toluene	Solubility***
LV-7*	Polybutene	300	50	Unlimited
HV-100*	Polybutene	1,000	50	2.47
HV-1900*	Polybutene	3,000	50	0.87
Tetlax 3T*	Polyisobutylene	66,000	50	0.7
LM-MH**	Polyisobutylene	85,000	50	0.66
Tetlax 5T*	Polyisobutylene	107,000	50	0.83
MM-L100**	Polyisobutylene	850,000	50	1.25
Acrylic	Polybutylacrylate	700,000	22	0.72
NR	Natural Rubber	1,000,000	35	1.38
*Nippon Petrochemical Company Limited
**Exxon Corporation
***ml of CO2 for 1 g of polymer solution at 800-900 psi at 27°/28° C.

[0022] A fluid PSA solution or dispersion is a necessary requirement for being able to apply the PSA in thin uniform continuous films on a substrate to be bonded.

Example II

[0023] In this example, the preparation of PSA adhesive compositions that are resistant to oils, fuels, and greases commonly found around transportation applications and environments is detailed. Such PSA adhesive compositions are based on PSA polymers prepared in either liquid CO2 or in supercritical CO2 from monomers that include a fluorinated monomer. These polymer preparations either utilized a thermal initiator (azobisisobutyronitrile) at elevated temperature (65° C.) or an organic redox initiator system (benzoyl peroxide and N,N-dimethyl aniline) at room temperature.

[0024] The polymers prepared below were synthesized from butyl acrylate (BA) and fluorinated octylmethacrylate (FOMA). The following results were recorded.

TABLE III
	Formulation		Molecular
Run No.	(weight parts)	Pressure	Weight	Polydispersity
1	BA/AIBN	3,000	357,000	3.36
	(100/1)
2	BA/AIBN	3,000	304,000	4.17
	(100/1)
3	BA/FOMA/AIBN	3,000	308,000	3.78
	(90/10/1)
4	BA/FOMA/AIBN	3,000	387,000	5.95
	(75/25/1)
5	BA/FOMA/AIBN	3,000	101,000	2.97
	(50/50/1)
6	BA/FOMA/AIBN	3,000	118,000	2.06
	(25/75/1)
7	BA/FOMA/AIBN	3,000	163,000	7.79
	(10/90/1)
8	BA/AIBN	1,500	334,000	6.00
	(100/1)
9	BA	600	137,000	3.42
	(Redox Initiator)

[0025] Not shown in these data is the ability of the liquid CO2 to stabilize the (co)polymerization process and, thus, create a more uniform product. For example, when polymerizing butyl acrlate in liquid CO2 as in Runs 1 and 2, the resulting polymer dispersion is characterized by large particles that settled out of the fluid. However, the fluorinated copolymer of Run No. was a fine dispersion of polymer that stayed in suspension in the CO2 fluid. Thus, it has been demonstrated that co(polymerization) of PSA polymers can take place in liquid or supercritical CO2 fluid without the presence of conventional volatile organic solvents. The art already demonstrates the advantages in application of coatings from fluid or supercritical CO2. These same advantages will be retained by the inventive PSAs of the present invention.

[0026] The properties of the new PSA polymers synthesized above are unique in that the fluorinated monomers control the degree of tack of the PSA and impart excellent mineral oil resistance to the system. Mineral oil resistance was chosen as a measure of PSA polymer resistance to oils, fuels, and greases commonly found around transportation applications and environments. The following data illustrate these properties.

TABLE IV
PSA System	Tack Value*	Mineral Oil Resistance
Polybutylacrylate Control	374	Severe attack in 10 minutes
(357,000 MW)
Polybutylacrylate Control	490	Severe attack in 10 minutes
(304,000 MW)
Run No. 3	476	Moderate attack after 30
		minutes
Run No. 5	157	No attach after 2 hours

[0027] These data demonstrate that the tack value can be controlled as can the mineral oil resistance of the PSA polymers by incorporating a fluorinated monomer in the polymer synthesis and by conducting the synthesis in either fluid CO2 or supercritical CO2.

Claims

1. In a method for making a pressure sensitive adhesive (PSA) wherein one or more of PSA monomer or oligomer reactants are subjected to polymerization, the improvement which comprises: subjecting said reactant to polymerization in a solvent of supercritical, near supercritical, or subcritical fluid.

2. The method of claim 1, wherein said fluid is carbon dioxide.

3. The method of claim 2, wherein said fluid is supercritical carbon dioxide.

4. The method of claim 3, wherein said supercritical carbon dioxide fluid is at 1500 psi.

5. The method of claim 1, wherein said reactants include a C1-C12 alkyl acrylate or methacrylate.

6. The method of claim 5, wherein said reactants include a fluorinated monomer or oligomer.

7. An improved pressure sensitive adhesive (PSA) composition, which comprises a PSA polymer dispersed in a solvent of supercritical, near supercritical, or subcritical fluid, and an organic cosolvent.

8. The PSA composition of claim 7, wherein said fluid is carbon dioxide.

9. The PSA composition of claim 8, wherein said fluid is supercritical carbon dioxide.

10. The PSA composition of claim 7, wherein said cosolvent is one or more of an ester which possesses the following characteristics: molecular weight range of 116-297, density range of 0.855-0.898, and χo factor (oxygen heteroatoms) of 0.108-0.275; an alcohol which possesses the following characteristics: molecular weight range of 144-186, density range of 0.827-0.831, and χo factor (oxygen heteroatoms) of 0.086-0.111; or a hydrocarbon which possesses the following characteristics: molecular weight range of 86-227, density range of 0.659-0.865, and χo factor (oxygen heteroatoms) of 0.

11. The PSA composition of claim 10, wherein said cosolvent is one or more of trans-2-hexenyl acetate, ethyl trans-3-hexanoate, methyl capronate, isobutyl isobutyrate, butyl acetate, butyl methacrylate, hexyl acetate, butyl butyrate, pentyl propionate, methyl enanthate, ethyl caproate, methyl dodecanoate, 2-ethylbutyl acetate, methyl oleate, dodecyl acetate, methyl tridecanoate, soybean oil methyl esters, hexane, heptane, tetradecane, hexadecane, toluene, 1-hexadecene, 1-dodecanol, 1-nonanol, and mixtures thereof.

12. A method for forming a stable dispersion of a pressure sensitive adhesive (PSA) polymer in a solvent of supercritical, near supercritical, or subcritical fluid, which comprises dispersing said PSA polymer in a mixture of said fluid and an organic cosolvent.

13. The method of claim 12, wherein said fluid is carbon dioxide.

14. The method of claim 12, wherein said fluid is supercritical carbon dioxide.

15. The method of claim 12, wherein said cosolvent is one or more of toluene, trans-2-hexenyl acetate, ethyl trans-3-hexanoate, methyl capronate, isobutyl isobutyrate, butyl acetate, butyl methacrylate, hexyl acetate, butyl butyrate, pentyl propionate, methyl enanthate, ethyl caproate, methyl dodecanoate, 2-ethylbutyl acetate, methyl oleate, dodecyl acetate, methyl tridecanoate, soybean oil methyl esters, hexane, heptane, tetradecane, hexadecane, 1-hexadecene, 1-dodecanol, or 1-nonanol.

16. A pressure sensitive adhesive (PSA) composition of improved mineral oil resistance, which comprises: a PSA polymer which is made from one or more of PSA monomer or oligomer reactants which are subjected to polymerization in a solvent of supercritical, near supercritical, or subcritical fluid, wherein said reactant includes a fluorinated monomer or oligomer reactant.

17. The method of claim 16, wherein said fluid is carbon dioxide.

18. The method of claim 17, wherein said fluid is supercritical carbon dioxide.

19. The method of claim 18, wherein said supercritical carbon dioxide fluid is at 1500 psi.

20. The method of claim 18, wherein said reactants include a C1-C12 alkyl acrylate or methacrylate.