TW203066B - - Google Patents

Description

Ry, 1) ¾ Γ, Π 6 5. Description of the invention () This novel invention relates to a high molecular weight ester copolymer resin. It has a low melting point and a turbid crystallization behavior and a procedure for preparing f-sealed grease. We can know that the molecular weight of the polyester resin can be increased by solid-state polycondensation reaction. The possibility of improving the polyester resin to have a low melting point, for example, below 220 ° C, there are many arduous procedural difficulties, because the adhesion on the reactor wall will be difficult due to the use of high temperatures The problem. · The well-known solid-state polycondensation procedures all require higher temperatures because the improved reactivity is too low. Generally, solid-state polycondensation reactions of polyesters are produced at temperatures above I80t: and most are above 195C (see Pag. 3295, Journal of Applied P oly ra. Sci. 2 8 3289-3300, 1989 ) The possibility of preparing some polyester resins with a low melting point and a sufficiently high limiting viscosity value and being particularly suitable for extrusion blowing applications is still an unsolved problem. Applicant's previous pending European application technology (N · 89119049.8) — — Printed by the solid state reform Ministry of Economic Affairs 屮 央 栉 准 ^ Α 工 消 作 Cooperative (please first ## 而 而 看 市 项 再 塡 写▲ ^ Good procedure is used to make dianhydrides using aromatic tetracarboxylic acid at modified temperature higher than 170 ° C. Usually it is made into resin in the range of 1 7 0 10 ~ 2 2 0 ° C. This modified resin is composed of a copolymer of ethyl terephthalate (C 0 PET s). In the use of C 0 PET s, for example, it is a copolymer of 10% mole percent. Its composition The unit is metabendioic acid. The scale of the acid paper used is ten. «Home« MCNS) < fM «m (21〇X2 < JV public it) HI. 7. 2U, U () () ik ( II) Λ 6 Π 6 A unit where the description of invention () is printed by the Zhengong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In addition to improving the melting point and ultimate viscosity of the resin, there is nothing special about the modified resin. We have now found that it is feasible to improve the resin so that its melting point is below 2 2 0 1C, without encountering the above-mentioned difficult problems and in particular, it greatly improves the biggest and most valuable difference from existing resins, that is, the crystallization behavior Different. The modified resin is a copolymer of terephthalic acid, containing 10 to 25%-weight percent of units derived from isophthalic acid. According to the procedure of this invention, C Ο Ρ Ε Τ improves the temperature below 1 70 ° C, and higher than the glass transition temperature seat (Tg) of the resin, usually add some aromatic, aliphatic chain, alicyclic hydrocarbon The dianhydrides of the tetracarboxylic acid, so that the temperature is between 130 and 1601C. Surprisingly, the modified resin is present in addition to the high limit millimeter IV value (higher than 0.85dl / g) and the melting point lower than 220 ° C. Nature. In particular, the crystallization behavior of this resin is very important in casting applications. Because this resin does not show any crystalline state by slowly cooling its melt, C 0 P E T s will show a clear transparent amorphous solid with a very slow cooling rate, such as l \: / inin. It is worth noting that when the resin is heated in the solid state, for example, it will crystallize into a solid state at 150 ° C for 40 minutes. The other interesting property is the non-condensation of the resin itself. It is interesting to note that C 0 PET is composed of a 15% replacement percentage of isophthalic acid (please read the back note first and then write this page j equipment-this paper standard uses the Chinese S standard ( CNS) A4 specifications (210X297 mm) 81. 7. 20,000 ^ (II), 030G〇Λ 6 It 6 V. Description of the invention (The melting point of the composition is 2 1 2 t :. This C Ο PET melts when slowly cooled (1 Ό / rain) will produce a clear and transparent amorphous solid. Pyromellitic anhydride is a more suitable modified compound. Other suitable dianhydrides are 1,2,3,4-cyclobutyltetracarboxylic acid Di-anhydrides with -3,4-dicarboxyl-1,2,3,4-tetrahydroxy-1-ansuccinic acid and 3,3 ', 4,4'-dibenzo-tetracarboxylic acid. The preferred dianhydride is 1,2,3,4 cyclobutane tetrahydroxy acid prepared from cyclic fatty acids. 3,4-dicarboxy-1,2,3,4-tetrahydroxy-1-naphthalene succinic acid and Dichen (2,2,2) oct-7-alkenyl-2,3,5,6-tetracarboxylic acid dianhydride can also get the same result. The more suitable additive concentration is 0 for polyester resin . 0 5 ~ 1 weight percent solid state improvement program contains several resins and additives that are mixed in the molten state, and convert the molten state into granules. It crystallizes above the Tg of the resin but below 180 °. The temperature range of this crystalline resin is approximately within 180 ° C and the Tg of the resin, and is usually 1 3 0 υ ~ 1 7 0 t :. First, pay attention to the market entry and fill out the original line. The Ministry of Economic Affairs, the Central Standards Bureau, ΚΞζ 工 消 " Cooperative Du Printed, and the moving one is opposite and the opposite is done to reverse the use of gas. The channel and crystal gas knots are radon-like, and the conjoined air transport heat is often added to the sequence. This resin tree is a good instrument for the program and the crystal structure is suitable for better operation. All the European-style photos are available according to the text and can be returned to the body, the gas is 8 I 7 sex 5 ί, the inertia is described in the response to the Chinese anti-test ® squeeze Xiansheng cultural production is available. 1 i, -fa , 1% by Wan Kelai agent 5 plus 40 to add 33 and 68 fat) 8 tree on cool ti poly ca companion • 11 0 81. 7. 20,000 < k (] l) This paper scale is easy to use in 8 Η family sample Standard (CNS) T4 specifications (210X297 male dragon; Λ 6 η 6 0; iQG6 V. Invention description () (Please read the notes before you fill in this page {set, such as synchronous rotation or Reverse-rotating screened or non-screened double-spiral extruders may have optional holes for venting, which can vary according to the melting point of polyester between 200T: and 350C. A double-spiral squeezing cylinder with reverse rotation and no screen, will be more suitable whether there are vent holes or not. The use of this type of squeeze cylinder can achieve a good distribution of additives in the melt, and can avoid the problem of some local additive concentrations becoming high due to their high reactivity. Extrusion can be fed directly from the molten COPET, which is formed by polycondensation from the molten state. Extrusion can also be used as solid COPET pellets in other factories. The extrusion cylinder is usually connected to a high vacuum oil pressure pump. The vacuum is maintained above 2 to to remove the volatiles of the active mixture. Resins containing low-level acetaldehyde, but the mixture can also be used without vacuum. The residence time in the extrusion cylinder can be between 10 and 120 seconds, usually 15 to 30 seconds. The Ministry of Economic Affairs, Central Bureau of Industry and Commerce, KK, Du Yin 5ί To avoid chaotic additive concentrations in the melt, we recommend additives diluted with crystalline polyethylene terephthalate (PET) powder (5 parts PE powder With 1 part of additive). This step can ensure a uniform distribution of the stearic tetracarboxylic acid dianhydride polymer (PMDA) in the melt, which leads to better product reproducibility of ultimate viscosity and non-condensing properties.

The dianhydrides can also be diluted with dianhydrides and crystalline PET pellets (10 copies of PET -6-this paper uses the National Beta National Standard (CNS) f 4 specifications (2) 0 > < 297 mm) ^ 81. 7. 20. _ Zhang (II) 03006 Λ 6 It 6 Printed by the Zhengong Consumer Cooperative of the Ministry of Economic Affairs, Biyang Bureau, Fifth, Description of Invention () 1 pair of additives). This diluent can be carried out with a leaf κ m mixer with 0.1% polyethylene glycol or polycaprolactone as an adhesive, and its search and mixing temperature is 150 ° C. This reactive melt is used by the double screw extrusion cylinder The submerged or strip-shaped granulation is continuously granulated. According to other aspects of this invention, the new COPETs will be modified by stirring some polymers, such as polybutylene terephthalate, polysulfonate, polycaprolactone, and polyelastomer. Or add Jin Dong 20% by weight of benzene gas-based resin before extrusion molding. This additive will produce an effect to improve the mechanical properties and processability of this composition without sacrificing the transparency of the resulting product. Analysis procedure The ultimate viscosity can be determined by a mixture of 0.5g COPET with 100®1 60/40 phenol and tetrachloroethane at 25T: according to ASTM D 4603-86. The content of acetaldehyde can be determined by ASTM D 4526-85 by gas chromatography, using Perkin Elmer 8700 gas analyzer. (Pe 「kin Elmer mode HS 101） The extraction status is 150C. 90 minutes. Example 1: 30kg / h of COPET melt (15% by weight isophthalic acid, melting point is 212¾. IV = 0.75dl / g) has 110PP Π1 of acetaldehyde (please read the notes on the back -4 fill in this page {this paper ft standard Xiao Yong Zhongqu β family sample standard (CNS) T4 regulation (210x297 public: ¢) 81. 7. 20,000 sheets (H ) .0¾ .0¾ Printed by the Ministry of Economic Affairs and printed by the A Cooperative Society ^ A () η ο__ V. The invention is called (). It is sent from the pilot plant of PET melt polycondensation to the reverse phase rotary screenless filter 30mm A double spiral extruded chrysanthemum with vent holes. 220g / h 20% by weight of pyromellitic acid in crystalline COPET powder (IV = 0.75 dl / g, 15% reset ratio of isophthalic acid) mixture It is fed into a squeeze cylinder with power transmission. The test conditions are as follows: • -Pyromellitic anhydride in COPET melt = 0.15% by weight-Rotation rate: 415 RPM.-Proportional length / diameter (L / D): 24 -Average residence time: 1 8-2 5 seconds-Jane temperature: 2 3 5 it-Product melting temperature: 290 it-Vacuum degree: 1-5 torr The die head with 2 holes is used for extrusion A pelletizer with a die head (diameter: 7 ram) is used to obtain COP ET granules, which have a cylindrical shape, a diameter of 3 nra and a length of 5π1 [π, with an ultimate viscosity of IV = 0.85 ± 0.01 d 1 / g 〇COPET The plate has acetaldehyde tongs 5 ~ 8ρριη. During the test, the IV value of the product will go through 2 weeks without change. The melting point of the product is 2 1 2 υ C [] Ρ Ε Τ 粒粒 箸 into the solid state improvement test factory, Use the instrument according to European application technology (European application> EP 86830340.5 and 81.1.7.2ϋ.000ίΜ! Ί)

L030GH Printed by the Ministry of Economic Affairs, Central Bureau of Labor and Development, β-Work Consumer Cooperatives V. Description of the invention () Inert gas reflux conditions. The crystallization temperature is 1 50 t and the residence time is 40 minutes. The temperature of the solid modified reactor is 150t. The residence time is 12h. The IV value of the improved product is 0.94 ± 0.02 dl / g. The product is non-gelatinous and has an acetaldehyde content of 0.60PPIII. In comparison, COPET does not contain pyromellitic anhydride (initial IV = 0.75 • d 1 / g). It is crystallized and improved under the same conditions as in the example. C Ο P E T has no improvement effect. The crystallization behavior of standard PET and COPET is shown in Figure 1. Figure 1 shows the crystallization kinetics of COPET prepared by the example compared to standard bottle grade polyethylene terephthalate. The crystallization kinetics is measured at a constant temperature of 120 = 0. Although COPET will crystallize in its solid state (150 C / 40fflin), its melt will not crystallize by cooling, but will form a clear by a very slow cooling rate Transparent amorphous solid skeleton. Table 1 shows the data related to COPET cooling example 1 while crystallization and standard PET comparison. All crystallization data were measured by the DS C measuring instrument of Mettler Thermal Analyzer YCII. Figure 2 describes the cooling rate of the DSC curve of COPET on the melt, starting from a rate of 10 scoops / 1114. The changes to 5 and 3/1/10 are curves A, B and C. Curve 1 shows that standard PET is cooled at a cooling rate of 10 / min, in which the heat of crystallization increases by 11.8J / g. _-9 -_ The national standard for pregnancy (CNS) r4 specification (2 丨 0X297 g: ¢) 81. 7. 20, U00ifcTll) (please note the written notes of Er'an ^ 1? -Γ ββ An V. Description of the invention () Table 1 The heat of fusion heat of the PET sample crystallized at different cooling rates is Joule / gram (.ioule / grara) The rapid cooling rate of the sample 10 5 3 C0PET quasi-PET 2.1 a 30.0 b N 34.1 0 Η Ν 間 1 ύ Contrary to it, the note is written by the Ministry of Economic Affairs, Bureau of Standards, Labor and Industry Cooperation, Duin 3i Η: no crystallization a) melting heat of crystallization 1.6 J / gb) melting crystallization Heat 2 9 · 1 J / gc) Melt heat of crystallization 12.2 J / g Example 2: 30kg / h CQPET melt (15% by weight isophthalic acid, melting point 2 1 2 t:, IV = 0 · 7 5 d 1 / g) The acetaldehyde Dong with 1 1 0 ρ ρ π was sent from the pilot plant of PET melt polycondensation to the reverse rotation, unscrewed 30ran exhaust with double spiral extrusion. 220g / h mixture of 1.2,3,4-cyclobutyltetracarboxylic dianhydride with 20% weight-to-exhaustion ratio in crystalline COPET powder (IV = 0.75 dl / s, 15% by weight isophthalic acid) was sent The squeeze of people conveyed by gravity. The test conditions are as follows: -10-The national standard (CNS) T4 specification (210X297 K; HI. 7. 2U.UU0 ^ (II), the standard of the Ministry of Economic Affairs, CS, CS, IV, and Co., Ltd.)印 3i V. Description of the invention ()-Cyclobutyltetracarboxylic dianhydride in the melt of COPE = 0.15% weight S percentage-Rotation rate: 415 RPM.-Proportional length / diameter (L / 1)): 2 4 -Average residence time · 1 8-2 5 seconds -Cylinder temperature: 235C • -Product melting temperature: 290D -Vacuum degree: 1-5 torr A die with 2 holes is used as an extrusion die (diameter: 7 mm) strip-shaped granulator is used to obtain C 0 PET granules, which have the shape of a graph column, a diameter of 3πη and a length of 5mn, and have an ultimate viscosity IV = 0.85 ± 0.01 dl / g. COPET particles have acetaldehyde set 5 ~ 8ρρπι. During the test, the IV value of the product will not change after 2 weeks. The melting point of the product is 212Ϊ: The COPPET pellets enter the solid-state improvement test plant, using equipment according to European application technology EP 86830340.5 and inert gas reflux conditions. The crystallization temperature is 150. The residence time is 40 minutes. The temperature of the solid modified reaction tank is 150t: and the residence time is 10h. The IV value of the improved product is 0.965 dl / g. The product is non-gel and its acetaldehyde fish content is 0.60 ppra. In comparison, C0PET does not contain pyromellitic anhydride (initial Π / = 0.75 d I / g). It is crystallized and improved with example phase conditions. C 0 PET is provided with improved _- II -_ This paper size is not used China Burmese family you fight (to 5) 1 »4 regulations (210X297 public < *) 81. 7. 2U, UU〇ik (ll) -ih Cooperative du printing 5. The role of invention description (). Example 3: The same COPET as in Example 1 is used in Example 3, but the IV value of crystalline COPET threshing is 0.75 dl / g. The crystalline COPET pellets are dried and sent to the double helix. The IV of the product is 0.84 5 ± 0.02 dl / g. • Under the same conditions as in Example 1, only the average residence time is 25 seconds. The solid state conditions are 130 ° ~ 140 t in the crystallization tank, and 140¾ in the polyaddition reaction tank. The residence time in the reaction tank was 10 hours. The ultimate viscosity of the granules is 0.92 ± 0.015 dl / g. Acetaldehyde content 0.67PPΠ. Example 4: The following table lists the extrusion blow molding conditions and the instrument molds used to produce 1500mi bottled products: rotary distributor / 2 mold tops: single-type embryo spiral length: 24 L / D spiral size: 6 5 mm Spiral type: Standard Polyvinyl Chloride (pvC) Objects: Figure bottle size: up to 1 5 0 0 m 1 Placement: 50.4kg / h (determined by bottle volume) Preform length: up to 4 0 cm -12-Original paper 5JL standard for easy use in the BBI family standard (CNS) T4 regulations (2 丨 0X297) "81. 7. 20.00Uik (ll) (please read ## while precautions before filling out this summer dress. Order_.V , λλι- 1-1Π positive 66 ΛΠ 5. Description of the invention () Yield: 9 6 0 bottles / hour (b 〇tt 1 es / h 〇u ") Period: S seconds Temperature squeeze: 2 5 0 ¾ pre-form : 2 8 0 1C Die: 2 9 0 Ό COPET water content after drying is less than 0.005%, using dry air with a De point between -30 * Ό and 401C.

The following table gives some blowing conditions, and the results are obtained from the COPET of Example 1. Read first. Read the notes on the back and then write

T Resin taste same / area part / die head bottle / hour bottle re-production set spiral rate ACA drip temperature r gr kg / h ΓΡΠ1 PPID test cm C0PET 230 270 280 960 42 50 ♦ 4 48 3.6 62 line of the Ministry of Economic Affairs The quasi-bureau A industrial and consumer cooperatives printed 3i aca 'Bm instance 5' ·

This example describes the COPET extruded according to the example before being mixed with polybutylene terephthalate (General Elect "U) (PBT 丨 blown IS; PBT -I 3- This paper is ft. Controversy (CNS) T4 regulation (210x297 public) 81. 7. 2U.UUUik (! L) Λ 6 It 6 ο The Ministry of Economic Affairs, Central Bureau of Industry and Commerce A industrial and consumer cooperation Du Yin ^ 3 i V. Invention description () The IV = 1.220dl / g is 3.5% of the total amount. The reset ratio is described in Example 4. This mixture is dried and blown. The following table gives the blowing conditions and results. Resin extrusion tube / top / die head temperature bottle / hour Γ 'Bottle weight gr output kg / h screw rate ΓΡΠ1 ACA ppm drip test era C0PET 240 280 300 960 42 50.4 52 3.7 70 Example 6: This example describes the polymerization according to Example 1 before blowing and squeezing and 5% reset percentage Dish. Cool mixing. (Dow.Chera). According to the description of Example 4, this mixture is dried and blown. The following table gives the blowing conditions and results. Resin extrusion cylinder / top / die bottle / hour bottle weight output spiral rate ACA drop temperature K ° gr kg / hr pm ppra test cm C0PET 240 290 300 960 42 50.4 52 3.7 70 -14- This paper is used in the "Eight Standards for Chess (CNS) Ή Regulations (210X29 / Public)" for free use in this paper. 81. 7. 2U.000i (c (II) (please fill in IVJI? Ben Ji.,

ο 3 ο M _Π6_ V. Description of the invention () Example 7: This example describes the mixing of benzene resin (Union Carbide) with 5% by weight before blowing extrusion according to Example 1. According to Example 4, the mixture is dried and blown. The following table gives the blowing conditions and results. (锖 先 读 #Considering precautions and then writing this book Λ resin extrusion tube / top / die bottle / hour bottle weight output spiral rate ACA drop temperature N0 gr kg / h ΓΡΠΙ PPH1 test cm C0PET 240 280 300 960 42 50.4 50 5.1 69

M-15 of the Employee Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs-Printed on this paper, using the Chinese National Qiping (CNS) T4 regulations (210X297 public goods) 81. 7. 20,000 ^ (11)

Claims (1)

Printed by the Ministry of Economic Affairs, Central Standard Staff Employee Cooperative :: '-Λ7 L one by one ......................: one by one: J B7 C7 D7 six 2. Patent application No. 81102405 "Copolyester Resin with Low Melting Point and High Molecular Weight" (Amended in January 1982) 1. An ethyl terephthalate copolymer, which contains 10 to 20 percent of replacement The resin composed of the derived units of m-dicarboxylic acid has an inherent viscosity higher than 0.85 dl / g and a melting point lower than 220t: and solidifies into an amorphous solid waist (cooling rate not lower than 11C / ioin). 2. Ethylene terephthalate copolymer as claimed in patent patent No. 1, which contains 15 weight percent resin of isophthalic acid units. 3. Ethylene terephthalate copolymer as claimed in item 1 or 2 of the patent patent application, which is non-condensable. 4. A method for producing an ethylene terephthalate copolymer as described in item 1 or 2 of Shenzhuang Patent Fan Garden, which comprises stirring a molten state of ethyl terephthalate copolymer and having an inherent viscosity of less than 0.85 dl / g, from 0.05 to 1 weight percent of aliphatic chain hydrocarbons, fatty hydrocarbons, aromatic dianhydride tetracarboxylic acid dianhydrides to form a melt, and then crystallize to improve the resin to make its temperature higher than T g and lower than 1 7 0 t :. 5. Ethylene terephthalate copolymer as claimed in item 1 or 2 of the patent application, in which 1-20% by weight is selected from polyacrylic acid ester. Polybutylene terephthalate, polymerization of Hun resin Thing. 6. A kind of article. The pseudo is prepared from the ethyl terephthalate copolymer as mentioned in items 1, 2, 3 or 5 of the patent application. 7. A kind of pedestal. Its 傜 is made by blowing the p-dibenzyl formate copolymer as described in Patent Application No.〗 〖2.3 or 5. This paper is again applicable to China National Standards (CNS) A 4 specifications (210 X 297 mm) --------------.-- {-------- installed- ----- Order {. Line (please read the notes on the back before writing this page)