Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2001-06-29
2002-04-16
Acquah, Samuel A. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S275000, C528S285000, C528S308100, C528S308300, C502S103000, C502S113000, C502S118000, C502S161000, C502S170000
Reexamination Certificate
active
06372879
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to synergistic combinations of titanium containing catalysts and catalyst enhancers of carboxylic acid or oxalic acid or their Li, Na, K, Rb. Cs, Be, Mg, Ca, St, Ba and ammonium salts that are useful for manufacturing polyesters. The synergistic combination of the titanium containing catalysts with a catalyst enhancer such as an oxalic acid, an oxalic acid salt or a carboxylic acid or a carboxylic acid salt provides fast reactions with improved properties such as reduced acetaldehyde content and good color properties for the resulting polyester at substantially reduced catalyst levels.
DESCRIPTION OF THE PRIOR ART
Polycondensation reactions that produce polyesters require an extremely long period of time that is significantly reduced by a suitable catalyst. Various types of catalysts are used to shorten the reaction time. For example, antimony trioxide, antimony triacetate and antimony trisglycoxide are generally used as polycondensation catalysts.
Titanyl oxalate compounds have been suggested as catalysts for polycondensation reactions to produce polyesters. However, titanyl oxalate catalysts when used as polycondensation catalysts for polyesters have caused color problems in the resulting polyester.
Polyesters are obtained by esterification, ester interchange or polycondensation of dibasic acids such as terephthalic acid and isophthalic acid or esters thereof, functional derivatives of acid chlorides and glycols such as ethylene glycol and tetramethylene glycol or oxides thereof and functional derivatives of carbonic acid derivatives. In this case, a single polyester is obtained when one dibasic acid component and glycol component are used. Mixed copolyesters can be obtained when at least two or more types of dibasic acid component and glycol component are mixed, esterified or subjected to ester interchange and then subjected to polycondensation. When a single polyester or two or more initial polycondensates of a mixed copolyester are subjected to polycondensation, an ordered polyester is obtained. In this invention, the term polyester is a general designation for these three types.
Prior literature has disclosed titanyl oxalate compounds for use as polycondensation catalysts for polyesters. The titanyl oxalate compounds disclosed include potassium titanyl oxalate, ammonium titanyl oxalate, lithium titanyl oxalate, sodium titanyl oxalate, calcium titanyl oxalate, strontium titanyl oxalate, barium titanyl oxalate, zinc titanyl oxalate and lead titanyl titanate. However, based upon the examples in such literature references, only potassium and ammonium titanyl oxalate have actually been used to catalyze the polyester forming reaction. See for example Japanese Patent Publication 42-13030, published on Jul. 25, 1967. European Patent application EP 0699700 A2 published Mar. 6, 1996 assigned to Hoechst and entitled “Process for production of Thermostable, Color-neutral, Antimony-Free Polyester and Products Manufactured From It” discloses the use as polycondensation catalyst, however only potassium titanyl oxalate and titanium isopropylate were used for such a catalyst, and, while improved color and antimony free polyester are disclosed, cobalt or optical brighteners were also employed. Other patents have disclosed potassium titanyl oxalate as a polycondensation catalyst for making polyester such as U.S. Pat. No. 4,245,086, inventor Keiichi Uno et al., Japanese Patent JP 06128464, Inventor Ishida, M. et al. U.S. Pat. No. 3,951,886, entitled “Process of Producing Polyester Resin” of Hideo, M. et al, at column 3, line 59 to column 4, line 10, contains a disclosure of titanyl oxalate catalysts for polyesters including a listing of many types of titanyl oxalate catalyst. However, only potassium titanyl oxalate and ammonium titanyl oxalate were used in the examples and lithium titanyl oxalate was not even listed among their preferred titanyl oxalate catalysts.
Titanium based catalysts have shown very high polycondensation activity, however; the resulted polyesters are yellowish color which will limit their applications. Therefore, prior art activity has been directed towards the development of modified titanium catalysts. Titanium compounds are not a good sole catalyst. Ti requires a cocatalysts or modifiers/promoters to form composite catalyst. Titanium compounds in the general formula of Ti(OR)
4
, Ti
(III)
Ti
(IV)
y
O
(3+4y)/2
, RO[Ti(OR)
2
O]
n
R have been widely claimed by others. Cocatalysts or modifiers/promoters, such as antimony compounds, tin compounds, zirconium compounds, silicon compounds, cobalt compound, aluminum compounds, alkali metal compounds, rare earth metal compounds, magnesium compounds, germanium compounds, zinc compounds, lanthanide series compounds, phosphorus compounds, halides, sulfur containing compounds, ammonia hydroxide, and amines, have been claimed together with Ti compounds.
U.S. Pat. No. 6,166,170, E. I. du Pont de Nemours and Company, issued on Dec. 26, 2000 discloses a catalyst composition of a titanium compound, a complexing agent, and an aqueous solution of hypophosphorous acid or a salt. The titanium compound has a general formula, Ti(OR)
4
, combined with a zirconium compound, Zr(OR)
4
. The complex agents are hydroxycarboxylic acids, alkanolamines, aminocarboxylic acids and their combinations of two or more.
U.S. Pat. No. 6,066,714, E. I. du Pont de Nemours and Company, issued on May 23, 2000, discloses an organic titanium compound, a phosphorus compound, an amine, and a solvent as a catalyst. The organic compound is Ti(OR)
4
. The phosphorus compound is either (RO)
x
(PO)(OH)
3−x
or (RO)
y
(P
2
O
3
)(OH)
4−y
. The amine is a tertiary amine. Aluminum, cobalt, antimony compounds and their combination were claimed as cocatalysts.
U.S. Pat. No. 6,034,203, E. I. du Pont de Nemours and Company, issued on Mar. 7, 2000, discloses a catalytic process that can be used in oligomerization, polymerization, or depolymerization. The catalyst has the formula of M
x
Ti
(III)
Ti
(IV)
y
O
(x+3+4y)/2
, where M is an alkali metal, such as Li; x and y are numbers greater than or equal to zero wherein if x equals zero, y is a number less than ½.
U.S. Pat. No. 5,981,690, E. I. du Pont de Nemours and Company, issued on Nov. 9, 1999. This patent shows a catalyst solution containing an organic titanate ligand, organic silicates and/or zirconates, and phosphorus compounds. Titanium has a formula of Ti(OR)
4
; silicon and zirconium compounds can be organic ortho silicate and zirconate; phosphorus compound can be an organic phosphonic or phosphinic acid. The solvent used was ethylene glycol. The catalyst was claimed to be used in fabrication of PET, PEI, PPT, PBT, and etc.
U.S. Pat. No. 5,866,710, Tioxide Specialties Limited, issued on Feb. 2, 1999 (EP 0 812 818 A1, published on Dec. 17, 1999). A process of preparing an ester is disclosed in the presence of a catalyst and a base, the product from orthoesters and condensed orthoesters of zirconium and titanium. The orthoesters have the formula of M(OR)
4
; the condensed orthoesters, RO[M(OR)
2
O]
n
R; where M is either zirconium or titanium. This compound can be illustrated as the following,
M(OR)
4
, if n=1
(RO)
3
MOM(OR)
3
, if n=2
(RO)
3
MOM(OR)
2
OM(OR)
3
, if n=3, and etc.
The base can be selected sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, magnesium hydroxide and ammonia.
WO 00/71252 A1, ACMA Limited, published on Nov. 30, 2000. An esterification catalyst composition was disclosed. The catalyst contains 1) hydrolysis product of orthoesters and condensed orthoesters of titanium, zirconium or aluminum; 2) an alcohol containing at least two hydroxyl groups; 3) an organophosphorus compound containing at least one P—OH group and a base; 4) a compound of germanium, antimony or tin.
WO 99/28033 A1, Tioxide Specialties, published on Jun. 10, 1999. An esterification catalyst composition was disclosed. The catalyst contains 1) hydrolysis product of orthoesters and conde
Chen Bin
Dowling Conor M.
Seshadri Sri R.
Acquah Samuel A.
ATOFINA Chemicals, Inc.
DeBenedicts Nicholas J.
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