JPH0420011B2 - - Google Patents

Description

[Detailed description of the invention]

Linear polyesters have only poor stability under the influence of UV radiation. One objective of the present invention is to improve the UV stability of linear polyesters. Linear polyester is a well-known thermoplastic polymer having a molecular chain formed by sequentially ester bonding glycol residues and dicarboxylic acid residues. Many acids and glycols have been proposed for the production of linear polyesters. Examples of such acids are (a) terephthalic acid, (b) isophthalic acid, (c) naphthalene-2,6-dicarboxylic acid, and (d) bis(carboxyphenoxy)ethane. Examples of glycols are alkanediols having 2 to 10 carbon atoms (eg ethylene glycol, 1,4-butanediol), and 1,4-dimethylolcyclohexane. The most common polyester is poly(ethylene terephthalate). Other industrial and commercially used linear polyesters include (a) mixtures of terephthalic acid and isophthalic acid (80-95 mol%
terephthalic acid) and ethylene glycol, (b) a copolymer of 1,4-butanediol and terephthalic acid, and (c) a copolymer of terephthalic acid and terephthalic acid.
There is a homopolymer with 4-dimethylolcyclohexane. The linear polyester according to the present invention contains an esterified residue of hydroxy-bis(hydroxy-alkoxy)xanth-9-one (hereinafter also referred to as "xanthone-9") in its molecule, and the amount of the esterified residue is 0.01~30wt based on total weight of polymer
%, preferably 0.05 to 5 wt%. Hydroxy-bis(hydroxy-alkoxy)
Xanthone-9 is preferably 1-hydroxy-
3,6-bis(hydroxy-alkoxy)xanthone-9, the alkoxy group preferably being
_C1 - _C10 alkoxy, more preferably _C2 - _C4 alkoxy (eg ethoxy) groups. The present invention has an intrinsic viscosity of 0.5 or more, and as a repeating unit -OYO-OC-XCO- [wherein X is component (a) (i) terephthalic acid, (ii) isophthalic acid, (iii) naphthalene- 2,6-dicarboxylic acid, (iv) bis(carboxyphenoxy)ethane, (v) aliphatic carboxylic acid having 4 to 50 carbon atoms in the molecule, Y is component (b) a glycol having 2 to 10 carbon atoms in the molecule, or a polymerized ether with a molecular weight of 150 to 3000 formed from one or more of these glycols, and (c) (a)+( 1-hydroxy-3,6-bis(hydroxy-alkoxy)xanthon-9-one in an amount of 0.01 to 30% by weight based on the sum of b) + (c). It relates to characteristic linear polyester. Important linear polyesters according to the invention have the following repeating units: -OYO-OC-X-CO- where at least 80 mol % of the X groups are p-
represents phenylene, the remainder represents m-phenylene, and at least 90 mol % of the Y groups are -C _o H _2o - (n is an integer from 2 to 10, e.g. -CH ₂
−CH ₂ −) and 0.01 based on the total polymer.
~30 wt% of the Y group represents the residue of 1-hydroxy-3,6-bis(hydroxyalkoxy)xanthone-9, which residue has the following formula 1: (In formula 1, n' and n'' are integers from 1 to 10, preferably from 2 to 4; for example, n'=n''=2). Other important elastomeric polyesters according to the invention have the following repeating units: -OYO-OC-X-CO- where at least 70 mol% of the X groups are p-
represents phenylene, and at least x of the X groups
The mol% represents the esterified residue of dicarboxylic acids having 4 to 40 carbon atoms in the molecule, and at least 70 mol% of the Y groups are -C _o H _2o - (n is an integer from 2 to 10) , e.g. −CH ₂ −CH ₂ −), and Y
At least y mol% of the groups are -(C _n H _2n O) _n ′C _n H _2n - (m is an integer from 2 to 10, m' is an integer from 2 to 50), for example -(C ₂ H ₄ O ) _n ″C ₂ H ₄ − − (C ₄ H ₈ O) _n ″ C ₄ H ₈ − (m″ is 15 to 45) and 0.01 to 30 wt%, preferably 0.05 to 5 wt % based on the total polymer %Y
The group represents a residue of 1-hydroxy-3,6-bis(hydroxyalkoxy)xanthone-9, which residue has the above formula 1, and n' and n'' are 1 to 1.
10 integers, e.g. n′=n″=2, and (x+
y) is at least 5. British Patent No. 924019 discloses that polymers and 1-
UV-resistant compositions comprising hydroxyxanthone stabilizers are described. The polymer may be, inter alia, a polyester, exemplified by polyethylene glycol terephthalate, and the 1-hydroxyxanthone compound may be, inter alia, 1,3,6-trihydroxyxanthone or 1-hydroxyxanthone. -3,6-bis-(β-hydroxyethoxy)xanthone. However, the polymer and stabilizer are merely physically mixed; there is no indication that the stabilizer is an integral part of the polymer. Our previous European patent application no.
Specification No. 6686 (published on January 9, 1980) states 3,
6-bis(hydroxyalkoxy)xanthone-
Polyesters containing residues of 9 compounds and similar to the polyesters of the present invention are described. Unexpectedly, we found that into linear polyester chains,
The residue of the hydroxy-bis(hydroxyalkoxy)xanthone-9 compound is used as a cross-linking agent that leaves one of its hydroxy groups unreacted and (as expected) eliminates the linearity of the polyester. We discovered that it can be introduced without causing any effects. Thus, the hydroxy groups of the xanthone compound that unexpectedly remain unreacted further improve the UV stability of the polymer composition. In the present invention, polyester has an intrinsic viscosity of
Must be greater than or equal to 0.5. The intrinsic viscosity is
“Polyester Fibrs,” by Hermann Ludewig.
"Chemistry and Technology" (Wiley-
Published by Interscience, 1971) Page 130, No. 18~
Measure as described in line 31. Same book No.
Equation (1) on page 126 shows the relative viscosity,
The intrinsic viscosity is derived from equations (2) and (3) described on the same page. As described in the same book, a 1:1 mixture of phenol and tetrachloroethane is used as the solvent for measuring the intrinsic viscosity. Measurements are carried out at 25°C. (Intrinsic viscosity is the basic viscosity
viscosity) or limiting viscosity
It is sometimes called. ) Linear polyesters are obtained in a two-step process. 1st
Precursors are made in stages. This precursor is a low molecular weight ester of a glycol and a dicarboxylic acid. In the second step, the precursor is polycondensed to increase its molecular weight, thereby obtaining a linear polyester. There are generally two ways to make such precursors. In the transesterification process, a glycol is reacted with a dialkyl ester of a dicarboxylic acid. Transesterification removes low molecular weight alcohols and produces glycol esters. For example, ethylene glycol is reacted with dimethyl terephthalate to produce ethylene glycol terephthalate and methyl alcohol, which is removed by distillation. The reaction rate can be increased by introducing a transesterification catalyst into the reaction mixture. A suitable transesterification catalyst is
Examples include zinc acetate, manganese acetate, calcium acetate, cobalt acetate, and titanium tetraisopropoxide. In the direct esterification method, a glycol and an acid are esterified to form a glycol ester while removing water. For example, ethylene glycol is esterified with terephthalic acid. Direct esterification is usually carried out without a catalyst.
However, under acidic conditions during direct esterification, ethylene glycol tends to dimerize through the reaction described below. 2HOCH ₂ CH ₂ OH → HOCH ₂ CH ₂ OCH ₂ CH ₂ OH + H ₂ O Some of the diethylene glycol produced by this reaction is introduced into the polymer chain, but a small amount can lower the softening point of the polymer. There are no negative effects other than a decline. The production of diethylene glycol involves direct esterification of alkaline compounds,
This can be reduced, for example, by the inclusion of sodium hydroxide, thus keeping the softening point at a satisfactory value. The second stage is carried out by heating the precursor under low pressure (for example below 5 mbar) and at a temperature above its melting point with stirring. During this polycondensation, glycol is liberated and is removed by distillation. As the reaction progresses, the molecular weight and viscosity increase. The increase in viscosity can be used as a means of confirming when the desired molecular weight has been achieved. Polycondensation catalysts are commonly used in this reaction. Suitable polycondensation catalysts include antimony trioxide, germanium dioxide, mixtures of both, titanium alkoxides, lead oxide and zinc. Some catalysts (eg germanium dioxide) are preferably dissolved in the alkali before being added to the reaction system. In such cases, it is particularly suitable to use the alkali present in the direct esterification stage to dissolve the catalyst (but in this way the catalyst does not directly influence the esterification reaction). Metals present during the reaction remain in the polymer, so when a colorless polymer is required,
It is necessary to avoid such residues being in the form of colored derivatives. Addition of phosphoric acids or esters thereof to the polycondensation reaction mixture can reduce the coloration caused by metals. Specific examples of phosphorous compounds suitable for addition to the polycondensation reaction mixture include orthophosphoric acid, triphenyl phosphate, and phosphorous acid. Our European Patent No. 6686 describes three methods for producing polyester. Two of these methods are applicable to the polyester of the present invention and are presented below. Method 1 According to method 1, the linear polyester, especially polyethylene terephthalate, is present in an amount of 0.04 to 10 wt%, preferably 0.04 to 5 wt%, based on the polymer to be produced.
A trihydroxyxanthone-9 compound, preferably the 1,3,6-isomer thereof, is added to either the precursor or the components for producing the precursor such that condensation occurs in the presence of the trihydroxyxanthone-9 compound. Manufactured by We found that when the trihydroxyxanthone-9 compound is included in the polycondensation reaction mixture, one hydroxyl group remains unreacted and the other two hydroxyl groups are present in the reaction system (bonded They discovered that the xanthone compound reacts with glycol (or unbonded) to form an ether bond, converting the xanthone compound into a bis(hydroxyalkoxy) derivative. This bis derivative forms an ester bond with an acid residue in the precursor. This overall reaction can be expressed as follows [here
HOOCACOOH stands for dicarboxylic acid, HOGOH stands for glycol and HOX(OH)OH stands for xanthone compound]. …AC(O)−OGOH+HOX(OH)OH+HOGO
−(O)CA… → …AC(O)−OG−O−X(OH)−O−GO−
(O)CA... Although the reaction mechanism is still not clear, the overall effect can be demonstrated for the following reasons. (a) No phenols can be extracted or detected in the polyester. (b) If the polyester is hydrolyzed to its acid and glycol components, hydroxyalkoxy derivatives of phenols are present in the hydrolyzate. (c) The results of spectral absorption analysis and nmr testing are consistent with the structure proposed for the product of the above reaction. A preferred method uses 1,3,6-trihydroxyxanthone-9, leaving its 1-hydroxyl group unreacted. Method 2 According to method 2, the linear polyester as described above is hydroxy-bis(hydroxyalkoxy)
xanthone-9 compounds, preferably 1,3,
The 6-isomer is made by incorporating either the precursor or the components for producing the precursor. A preferred alkoxy group is an ethoxy group. Method 2 is particularly suitable for the production of polyesters using glycols other than ethylene glycol, such as polybutylene terephthalate. The polyester according to the invention can be made into shaped articles with good UV stability. Shaped articles include fibers and films, such as metallized films and coextruded laminates having one or both outer layers of the polyester of the present invention. Metallized films can be used as reflectors in solar energy collectors. The transparent film can be used as a transparent cover material for windows, greenhouses, gardening, solar cells, etc. Shaped articles can be made entirely of the polyester of the invention or from blends of the polyester of the invention and conventional polyesters. The production of the polyester of the present invention will be exemplified below.
In the following examples, 1,3,6-trihydroxyxanthone-9 is abbreviated as "136THX". Example 1 This example illustrates the preparation of a linear polyester according to the invention using a two-step process consisting of (1) direct esterification followed by (2) polycondensation.
The following reactants were charged to the autoclave to begin step (1). 60.5Kg Terephthalic acid 30 Ethylene glycol 3.5g Germanium dioxide 3.5g Sodium hydroxide For convenience of handling, the above GeO ₂ and
Both NaOH were dissolved together in a small amount (approximately 50 g) of the above ethylene glycol. The autoclave was pressurized to about 3 atmospheres,
Heat with stirring. The reaction started and the esterification reaction product water was removed along with some of the excess glycol. The temperature was maintained at reflux. All of the water produced by the esterification reaction was removed in about 2.5 hours, at which point the temperature had risen to 248°C. The pressure was released for about 5 minutes and a small amount (about 5) of glycol was removed. This completed the direct esterification (conventional method). Then 119 g of triphenyl phosphate (as a methanol solution) were added. 77 kg of product were obtained, which is a customary precursor for the production of polyethylene terephthalate. This was used in the following polycondensation. The precursor was transferred to a polycondensation reaction vessel and prepared for step (2). Polycondensation was initiated by adding 2100 g (ie 2.7 wt% relative to the precursor) of 136THX and 21 g of antimony trioxide. Glycol removal was initiated by distillation at 230°C with stirring under atmospheric pressure. When the distillation started, the pressure was gradually reduced to 0.3 mbar and the temperature was maintained at 290°C. The pressure was returned to atmospheric and the polymer was removed from the polycondensation reaction vessel and cut into small pieces. The total weight of the polymer was 61Kg. The manufacturing method described in this example can be said to be conventional except for the addition of 136THX. The resulting polymer was film-forming grade poly(ethylene terephthalate). It contained 3% by weight based on the weight of the polymer of 1-hydroxy-3,6-bis(oxyethoxy)xanthone-9 residues, i.e., n'=n''=2 in Formula 1 above. Example 2 This example also illustrates the production of a linear polyester of the present invention using a two-step process consisting of (1) direct esterification followed by (2) polycondensation, but in this example 136THX was Added at the start of direct esterification. The following reactants were charged to the autoclave to start step (1): 60.5Kg Terephthalic acid 1.4Kg 136THX 30 Ethylene glycol 3.5g Germanium dioxide 3.5g Sodium hydroxide Handling convenience GeO ₂ and
NaOH was co-dissolved in a small amount (approximately 50 g) of ethylene glycol. The autoclave was pressurized to about 3 atmospheres and heated with stirring. The reaction started and the esterification product water was removed along with some of the excess glycol. The temperature was maintained at reflux. All esterification product water is removed in approximately 2.5 hours, at which point the temperature is
The temperature had risen to 248℃. Release the pressure in about 5 minutes,
A small amount (approximately 5) of glycol was removed. This completes the direct esterification (conventional method) and then
119 g of triphenyl phosphate (as a methanol solution) were added. During this direct esterification some of the 136THX will probably be esterified to the hydroxyethoxy derivative.
Since there is an excess of hydroxy groups in the reaction mixture, the xanthone derivative competes with the ethylene glycol and an equal amount of it is introduced into the precursor. 77Kg of precursor was obtained. This was used in the polycondensation step described below. This was a conventional precursor except for the xanthone derivative. The 136 THX that did not react during this first stage reacts during the second stage. The precursor is then transferred to a polycondensation vessel and the step
(2), prepared by adding 21 g of antimony trioxide for the polycondensation reaction. Glycol removal was started at 230°C under atmospheric pressure with stirring. When the distillation started, the pressure was gradually reduced to 0.3 mbar and the temperature was maintained at 290°C. The pressure was returned to atmospheric and the polymer was removed from the polycondensation vessel and cut into small pieces.
The total weight of the polymer was 61Kg. The manufacturing method in this example can be said to be conventional except for the addition of 136THX. The polymer is film-forming grade poly(ethylene terephthalate).
It was hot. It contains 2wt% based on the weight of the polymer of 1-hydroxy-3,6-bis(oxyethoxy)xanthone-9 residues having the formula 1 (n′=n″=2). Examples 3-9 These examples demonstrate the presence of esterified residues of 136THX according to the present invention in elastomeric polyesters.
and products containing conventional aliphatic acids and polyglycols. The polyglycols used are poly(ethylene glycol (abbreviated as PEG)) and poly-1,4-butanediol (abbreviated as PBG), which have molecular weights of 1000 and 2000, respectively, as shown in Table 1. Ta.

[Table] As aliphatic carboxylic acids, (a) a composition sold by Unilever Emery under the trade name "EMPOL1014" and (b) azelaic acid were used. Note that "EMPOL1014" is an aliphatic dicarboxylic acid with a molecular weight of approximately 500 to 700, but its details are not available. A polyester was prepared in the same manner as described in Example 2. At this time, the autoclave was charged with the reactants shown in Table 2.

【table】

[Table] 119 g of triphenyl phosphate (as methanol solution) and 21 g after direct esterification reaction
g of antimony trioxide and Example 2
The production was completed by polymerization as follows. In each of Examples 3-9, the product was a film-forming grade polyester. Compared to conventional PET, each product had improved UV stability and lower elastic modulus.

Claims (1)

[Claims] 1. has an intrinsic viscosity of 0.5 or more, and has -OYO-OC-XCO- as a repeating unit [wherein X is component (a) (i) terephthalic acid, (ii) isophthalic acid, (iii) ) naphthalene-2,6-dicarboxylic acid, (iv) bis(carboxyphenoxy)ethane, (v) aliphatic carboxylic acids having 4 to 50 carbon atoms in the molecule, dicarboxylic acids selected from (b) a glycol having 2 to 10 carbon atoms in the molecule, or a polymeric ether with a molecular weight of 150 to 3000 formed from one or more of said glycols, and (c) (a )+(b)+(c) in an amount of 0.01 to 30% by weight based on the sum of 1-hydroxy-3,6-bis(hydroxy-alkoxy)xanth-9-one] A linear polyester characterized by having: 2 The alkoxy group in 1-hydroxy-bis(hydroxy-alkoxy)xanth-9-one is 2
A linear polyester according to claim 1 having ˜4 carbon atoms. 3 As a repeating unit, -OYO-OC-X-CO- [wherein at least 80 mol% of the X groups represent p-phenylene and the remainder represent m-phenylene, and at least 90 mol% of the Y groups represent -C _o H _2o −(n
represents an integer of 2 to 10), and 0.01 to 30% by weight based on the total polymer of Y group represents the following formula (n' and n'' are integers of 1 to 10) The linear polyester according to claim 1 or 2, which has the following structure: -OYO-OC-X as a repeating unit. -CO- [wherein at least 70 mol % of the X groups represent p-phenylene, at least x mol % of the X groups are formed from dicarboxylic acids having 4 to 40 carbon atoms in the molecule, and At least 70 mol% is −
C _o H _2o - (n is an integer from 2 to 10), and at least y mol% of the Y group is -(C _n H _2n O) _n ′C _n H _2n - (m is an integer from 2 to 10,
m' represents an integer from 2 to 50), and (x+y)
is at least 5, based on the total polymer of Y groups
For 0.01 to 30% by weight, use the following formula (n′ and n″ are integers from 1 to 10).]
A linear polyester according to any one of claims 1 to 3. 5. The linear polyester according to claim 3 or 4, wherein -C _o H _2o - is -CH ₂ CH ₂ -. 6. The linear polyester according to any one of claims 3 to 5, where n'=n''=2.7 The formula -(C _n H _2n O) _n 'C _n H _2n - is , −(C ₂ H ₄ O) _n ″C ₂ H ₄ − or −(C ₄ H ₈ O) _n ″C ₄ H ₈ − (in the formula, m″ is 15 to 45)
The linear polyester according to any one of claims 4 to 6. 8 has an intrinsic viscosity of 0.5 or more and as a repeating unit -OYO-OC-XCO- [wherein X is component (a) (i) terephthalic acid, (ii) isophthalic acid, (iii) naphthalene-2,6 - dicarboxylic acids, (iv) bis(carboxyphenoxy)ethane, (v) aliphatic carboxylic acids having 4 to 50 carbon atoms in the molecule, where Y is a component (b) glycols having 2 to 10 carbon atoms in the molecule, or polymeric ethers with a molecular weight of 150 to 3000 formed from one or more of these glycols, and (c) (a)+(b)+ 1-hydroxy-3,6-bis(hydroxy-alkoxy)xanth-9-one in an amount of 0.01 to 30% by weight based on the sum of (c) Component (a) or its dialkyl ester and component (b)
together with 1, 3, 6 at a temperature of 230 to 290℃.
-trihydroxy-xanthon-9-one, whereby one 1-hydroxy group of the trihydroxyxanthone remains unchanged and the other two hydroxyl groups react with component (b) to form an ether. A method characterized by forming a bond. 9 has an intrinsic viscosity of 0.5 or more, and as a repeating unit -OYO-OC-XCO- [wherein X is component (a) (i) terephthalic acid, (ii) isophthalic acid, (iii) naphthalene-2,6 - dicarboxylic acids, (iv) bis(carboxyphenoxy)ethane, (v) aliphatic carboxylic acids having 4 to 50 carbon atoms in the molecule, where Y is a component (b) glycols having 2 to 10 carbon atoms in the molecule, or polymeric ethers with a molecular weight of 150 to 3000 formed from one or more of these glycols, and (c) (a)+(b)+ 1-hydroxy-3,6-bis(hydroxy-alkoxy)xanth-9-one in an amount of 0.01 to 30% by weight based on the sum of (c) 1-hydroxy-3,6-bis(hydroxy-alkoxy)xanth-9-one by combining component (a) or its dialkyl ester with component (b) at a temperature of 230 to 290°C. A process characterized in that the 1-hydroxy group remains unchanged and the two hydroxy-alkoxy groups participate in the polyester-forming reaction.