CN107892744A - A kind of preparation method of Heat Shrinkage Film Polyester section - Google Patents
A kind of preparation method of Heat Shrinkage Film Polyester section Download PDFInfo
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- CN107892744A CN107892744A CN201711189560.6A CN201711189560A CN107892744A CN 107892744 A CN107892744 A CN 107892744A CN 201711189560 A CN201711189560 A CN 201711189560A CN 107892744 A CN107892744 A CN 107892744A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a kind of preparation method of Heat Shrinkage Film Polyester section, it is using terephthalic acid (TPA), modifier glycol, ethylene glycol, modified binary acid as major ingredient, in the presence of Compositional type auxiliary agent, it is made through substep mashing, low temperature fractional esterification, polycondensation and pelletizing.By the way that the modified copolyester form and aspect of the inventive method production are excellent, heat-shrinkable is good, melting range is short, otherness is small between product batches.
Description
Technical field
The invention discloses a kind of preparation method of heat shrink films special polyester chip, belongs to co-polymerization modified polyester production neck
Domain.
Background technology
Heat shrink films are widely used in the packaging industry of beverage and commodity etc., and it is mainly prepared by PVC, PS.PVC heat
Shrink film has the characteristics of transparency is high, glossiness is good, shrinkage factor is high, but because beverage bottle mostly be PET materials, need during regeneration
PVC labels are removed, process is cumbersome, and effective chlorine be present, directly affects environmental protection.PS thermal contractive label films are similarly present
The cumbersome phenomenon of regenerative process.The polyester product (PETG) that 1,4 cyclohexane dimethanol is modified at present is highly suitable for heat shrink films
Preparation, but due to its raw and auxiliary material 1,4-CHDM (CHDM) production technology at present only have two companies grasp, point
Wei not the SK of the South Korea and Yi Siman in the U.S..Domestic production PETG is needed to buy expensive raw and auxiliary material CHDM, and accounting is produced into
Price is higher than the imported product of same type after this.
The country also has some by producing the research of heat shrink films special polyester chip to polyester modification, but is respectively provided with certain
Defect.The second modification list is introduced on the basis of the monomer modified PET of neopentyl glycol as patent CN102807669A discloses one kind
Body dicarboxylic acids, by introducing melt reinforcing agent, gathers copolymerization to improve the heat-shrinkable of the modified monomer of neopentyl glycol single
Ester molecule produces branched and partial cross-linked PET conglutination and intensity, but because esterification temperature is higher in the modified poly ester production process
Cause side reaction more, have a strong impact on the form and aspect of product.Patent CN104327256A, which discloses a kind of modified heat shrink films and used, to be gathered
The production technology of ester section, using three kettle flows：Esterification → precondensation → final minification gathers, and the section heat for optimizing each point technique productions is received
Contracting is good, inherent viscosity is high, form and aspect are good, quality is homogeneous, but neopentyl glycol esterification is esterified compared with ethylene glycol in actual production process
It is relatively slow, neopentyl glycol be difficult whole blocks into strand, cause product thermal contraction performance between batch to differ larger,
This mainly due between batch the reason for product institute neopentyl glycol containing content difference it is caused, additionally, due in polycondensation process new penta
Glycol largely takes off from polycondensation vessel, increases subsequent treatment expense, and not environmentally.
The content of the invention
The invention provides a kind of preparation method of Heat Shrinkage Film Polyester section, it is intended to obtains alternative PETG products
Modified polyester chips.
The present invention adopts the following technical scheme that to realize goal of the invention：
The preparation method of Heat Shrinkage Film Polyester of the present invention section, be with terephthalic acid (TPA), modifier glycol, ethylene glycol,
Modified binary acid is major ingredient, in the presence of Compositional type auxiliary agent, is made through substep mashing, low temperature fractional esterification, polycondensation and pelletizing
Heat Shrinkage Film Polyester is cut into slices；
The modifier glycol is at least one in neopentyl glycol, 1,3- propane diols, the amylalcohol of season four, diethylene glycol (DEG) and triethylene glycol
Kind, preferably neopentyl glycol；Ensure shrinkage to suppress the crystal property of copolyesters, the addition of the modifier glycol accounts for institute
State 5wt%~30wt% of terephthalic acid (TPA) weight, preferably 10wt%~20wt%.
The addition of the ethylene glycol accounts for 30wt%~40wt% of the terephthalic acid (TPA) weight.
The modified binary acid is M-phthalic acid and/or phthalic acid, preferably M-phthalic acid；To ensure low temperature
Thermal contraction effect, the addition of the modified binary acid account for 3wt%~20wt% of the terephthalic acid (TPA) weight, are preferably
5wt%~15wt%.
The Compositional type auxiliary agent is acidic materials and buffer salt material in mass ratio 1~5：1 mixture formed, it is described multiple
The addition of distribution type auxiliary agent accounts for 0.5wt%~1.5wt% of modifier glycol weight；The acidic materials are sulfuric acid, phosphoric acid, lemon
The serial lewis acids such as lemon acid, p-methyl benzenesulfonic acid, butyl titanate or tetrabutyl zirconate, the buffer salt material be sodium acetate,
Sodium phosphate, disodium hydrogen phosphate or sodium dihydrogen phosphate.Preferably, the Compositional type auxiliary agent is the compounding of p-methyl benzenesulfonic acid and sodium acetate
Thing.The Compositional type auxiliary agent can be catalyzed the esterification of neopentyl glycol and terephthalic acid (TPA) at low temperature, and and can suppresses side reaction
Generation,
Specifically, the preparation method of Heat Shrinkage Film Polyester section of the present invention, comprises the following steps：
Step 1, substep are beaten
Part terephthalic acid (TPA) and modifier glycol and Compositional type auxiliary agent are added in high temperature mashing kettle, 100 DEG C~150 DEG C
(preferably 110 DEG C~140 DEG C, further preferred 120 DEG C~130 DEG C) melting mixing is uniform；
Remainder terephthalic acid (TPA) and ethylene glycol, modified binary acid are added into normal temperature mashing kettle, stirred；
During specific addition, it is beaten in high temperature in kettle, the mol ratio of modifier glycol and terephthalic acid (TPA) is 1.15~1.25:
1；It is beaten in normal temperature in kettle, the mole of ethylene glycol and the ratio between terephthalic acid (TPA) and modified binary acid integral molar quantity be 1.15~
1.25:1。
Step 2, low temperature fractional esterification
The first step is esterified：It is by esterification temperature in material the first esterifying kettle of feeding after high temperature mashing kettle processing, is controlled
200 DEG C~250 DEG C (preferably 210 DEG C~240 DEG C, further preferred 220 DEG C~230 DEG C)；Normal pressure heat-insulating 30min is completed in charging,
Then the material added after normal temperature mashing kettle processing, and continue normal pressure heat-insulating 30min after the completion of charging；
Second step is esterified：After the esterification of the first esterifying kettle terminates, material is sent into second esterification kettle, temperature of charge is steady
Determine to 205 DEG C~215 DEG C, then add the modifying agent polyethylene glycol for accounting for raw material terephthalic acid (TPA) weight 5wt%~10wt%, together
When add and account for the antimony system polycondensation catalyst of raw material terephthalic acid (TPA) weight 0.03%~0.08%, then heat to 225 DEG C~245
DEG C, 30~90min of normal pressure esterification；The weight average molecular weight of the modifying agent polyethylene glycol is 600~4000.
Step 3, polycondensation and pelletizing
After second step esterification terminates, routinely technique carries out carry out polycondensation, pelletizing, that is, obtains Heat Shrinkage Film Polyester and cut
Piece finished product.
Compared with existing technology, the beneficial effects are mainly as follows：
1st, using the method for the present invention, the dihydric alcohol and binary acid larger by being rationally copolymerized steric hindrance, copolymerization is suppressed
The crystal property of ester, the heat shrink films special polyester chip similar to PETG performances is produced, solved domestic heat at present and receive
Uneven, the product hue difference of contracting film special polyester chip modified monomer polymerization, percent thermal shrinkage are low, quality fluctuation is big between batch products
The problem of.
2nd, the present invention realizes terephthalic acid (TPA) and modifier glycol (new penta 2 using substep mashing, substep esterification technique
Alcohol) react in advance, dibasic acid esters structure is formed, makes modifier glycol homogeneous blocks into each strand；Formed after dibasic acid esters structure,
Terephthalic acid (TPA), ethylene glycol, modified binary acid, polyethylene glycol are added, copolymerization forms stable molecular structure, avoids the later stage from changing
The effusion of property dihydric alcohol (neopentyl glycol), influences thermal contraction performance.
3rd, the present invention realizes low temperature esterification, solves neopentyl glycol copolyesters and easily turn yellow by using Compositional type auxiliary agent
The problem of.
4th, the modified copolyester form and aspect that are produced by this patent method are excellent, heat-shrinkable is good, melting range is short, product batches it
Between otherness it is small.
Embodiment
Technical scheme is elaborated with reference to embodiment, following embodiments are with the technology of the present invention side
Implemented under premised on case, give detailed embodiment and specific operating process, but protection scope of the present invention is not
It is limited to following embodiments.
Embodiment 1
The present embodiment following steps for manufacturing Heat Shrinkage Film Polyester is cut into slices：
1st, substep pulping process
High temperature is beaten kettle：814kg neopentyl glycols are put into high temperature mashing kettle, temperature are to slowly warm up to 110 DEG C, constant temperature
After 30min, click on and start stirring motor, it is abundant slowly to put into 1100kg terephthalic acid (TPA)s, 3kg p-methyl benzenesulfonic acid, 2kg sodium acetates
Stir.
Normal temperature is beaten kettle：1720kg ethylene glycol is put into normal temperature mashing kettle, starts stirring motor, slowly input
3650kg terephthalic acid (TPA)s, 250kg M-phthalic acids, are stirred.
Step 2, low temperature fractional esterification
The first step is esterified：Material after high temperature mashing kettle processing is slowly at the uniform velocity sent into the first esterifying kettle by gear pump
In, temperature keeps 225 DEG C ± 2 DEG C, 102 DEG C ± 2 DEG C of capital segregator temperature holding in the first esterifying kettle；Material normal pressure heat-insulating 30 is entered
Minute, the material then added with same operating procedure after normal temperature mashing kettle processing, all enter normal pressure heat-insulating 30 after material
Minute, gained esterifying liquid imports second esterification kettle using nitrogen；
Second step is esterified：After material imports second esterification kettle, into second esterification kettle, addition 300kg weight average molecular weight is
2000 PEG and polycondensation catalyst glycol antimony catalyst 3kg, temperature ensures at 210 DEG C ± 2 DEG C, after adding when adding PEG
Start heating schedule and temperature is slowly risen to 235 DEG C, class time control is 90min.
Step 3, polycondensation and pelletizing
Material imports synthesis under normal pressure 10min after polycondensation vessel after second step is esterified, and vacuumizes while starts heating schedule, contracts
Poly- 285 DEG C of final temperature, polycondensation total reaction time 260 minutes, the low liter of stage control that 1.5Kpa is evacuated to from normal temperature is 60min, pressure
Control and reacted to enter high vacuum after 1.5Kpa, it is 10pa to continue to be evacuated to Stress control, and constant pressure reaction, discharge power
35kw。
Embodiment 2
The manufacture craft of the present embodiment polyester slice is same as Example 1, differs only in step 1 and enters as follows
OK：
1720kg ethylene glycol is put into being beaten in kettle, after 814kg neopentyl glycols are sufficiently stirred, and slowly puts into 4750kg to benzene
Dioctyl phthalate, 250kg M-phthalic acids, 3kg p-methyl benzenesulfonic acid, 2kg sodium acetates, are stirred, and are beaten using a step normal temperature.
Embodiment 3
The manufacture craft of the present embodiment polyester slice is same as Example 1, differs only in and does not add Compositional type auxiliary agent.
Embodiment 4
The manufacture craft of the present embodiment polyester slice is same as Example 3, differs only in the temperature control of first step esterification
It is made as 250 DEG C ± 2 DEG C.
Embodiment 5
The manufacture craft of the present embodiment polyester slice is same as Example 1, differ only in step 1 p-methyl benzenesulfonic acid and
Sodium acetate with the addition of respectively 6kg, 4kg.
Process conditions and products obtained therefrom the performance parameter contrast of above-described embodiment are shown in Table 1.
Table 1：The performance parameter test of modified copolyester section prepared by embodiment 1-5 is as follows：
Method of the invention is optimal case as can be seen from the above data, and work is esterified using substep mashing, low temperature fractional
Skill, contribute to the preferable block distributed of neopentyl glycol in each strand, and the melting range span of product is small, neopentyl glycol content
Height, product form and aspect are good, percent thermal shrinkage is high, can substitute PETG products completely.Using other schemes, such as high temperature, excessive auxiliary agent all
Side reaction can be caused to increase, the form and aspect for being embodied in product are high, neopentyl glycol content is low, melting range span is larger, are unfavorable for producing
The following process of product and application.
The exemplary embodiment of the present invention is these are only, is not intended to limit the invention, all spirit in the present invention
With all any modification, equivalent and improvement made within principle etc., it should be included in the scope of the protection.
Claims (6)
- A kind of 1. preparation method of Heat Shrinkage Film Polyester section, it is characterised in that：Be with terephthalic acid (TPA), modifier glycol, Ethylene glycol, modified binary acid are major ingredient, in the presence of Compositional type auxiliary agent, through substep mashing, low temperature fractional esterification, polycondensation and are cut The obtained Heat Shrinkage Film Polyester section of grain；The modifier glycol is at least one of neopentyl glycol, 1,3- propane diols, the amylalcohol of season four, diethylene glycol (DEG) and triethylene glycol； The addition of the modifier glycol accounts for 5wt%~30wt% of the terephthalic acid (TPA) weight；The addition of the ethylene glycol accounts for 30wt%~40wt% of the terephthalic acid (TPA) weight；The modified binary acid is M-phthalic acid and/or phthalic acid, and it is described right that the addition of the modified binary acid accounts for 3wt%~20wt% of phthalic acid weight；The Compositional type auxiliary agent is acidic materials and buffer salt material in mass ratio 1~5：1 mixture formed, the Compositional type The addition of auxiliary agent accounts for 0.5wt%~1.5wt% of modifier glycol weight；The acidic materials are sulfuric acid, phosphoric acid, lemon Acid, p-methyl benzenesulfonic acid, butyl titanate or tetrabutyl zirconate, the buffer salt material are sodium acetate, sodium phosphate, disodium hydrogen phosphate Or sodium dihydrogen phosphate.
- 2. preparation method according to claim 1, it is characterised in that：The modified binary acid is M-phthalic acid, and the addition of the modified binary acid accounts for the terephthalic acid (TPA) weight 5wt%~15wt%；The modifier glycol is neopentyl glycol, and the addition of the modifier glycol accounts for the terephthalic acid (TPA) weight 10wt%~20wt%.
- 3. preparation method according to claim 1 or 2, it is characterised in that：The acidic materials are toluenesulfonic acid, described slow It is sodium acetate to rush salt material.
- 4. preparation method according to claim 1, it is characterised in that specifically comprise the following steps：Step 1, substep are beatenPart terephthalic acid (TPA) and modifier glycol and Compositional type auxiliary agent are added in high temperature mashing kettle, 100 DEG C~150 DEG C meltings It is well mixed；Remainder terephthalic acid (TPA) and ethylene glycol, modified binary acid are added into normal temperature mashing kettle, stirred；Step 2, low temperature fractional esterificationThe first step is esterified：Material after high temperature mashing kettle processing is sent into the first esterifying kettle, it is 200 DEG C to control esterification temperature ~250 DEG C；Normal pressure heat-insulating 30min is completed in charging, the material then added after normal temperature mashing kettle processing, and after the completion of charging Continue normal pressure heat-insulating 30min；Second step is esterified：After the esterification of the first esterifying kettle terminates, material is sent into second esterification kettle, temperature of charge is stable extremely At 205 DEG C~215 DEG C, the modifying agent polyethylene glycol for accounting for raw material terephthalic acid (TPA) weight 5wt%~10wt% is added, is added simultaneously The antimony system polycondensation catalyst of raw material terephthalic acid (TPA) weight 0.03%~0.08% is accounted for, then heats to 225 DEG C~245 DEG C, often 30~90min of pressure esterification；Step 3, polycondensation and pelletizingAfter second step esterification terminates, polycondensation, pelletizing are carried out by with conventional polyester product processes identical common process, i.e., Obtain Heat Shrinkage Film Polyester section finished product.
- 5. preparation method according to claim 4, it is characterised in that：In step 1：It is beaten in high temperature in kettle, modified binary The mol ratio of alcohol and terephthalic acid (TPA) is 1.15~1.25:1；It is beaten in normal temperature in kettle, the mole of ethylene glycol and terephthaldehyde The ratio between acid and modified binary acid integral molar quantity are 1.15~1.25:1.
- 6. preparation method according to claim 4, it is characterised in that：In step 2, the weight of the modifying agent polyethylene glycol is equal Molecular weight is 600~4000.
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| CN201711189560.6A CN107892744B (en) | 2017-11-24 | 2017-11-24 | A kind of production method of Heat Shrinkage Film Polyester slice |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790907A (en) * | 2019-11-18 | 2020-02-14 | 扬州普立特科技发展有限公司 | Production equipment and process flow of full-continuous PETG |
| CN112679709A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyester for heat shrinkable film and preparation method thereof |
| CN114426661A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Polyester for high-antistatic heat-shrinkable film and preparation method thereof |
| CN115232293A (en) * | 2022-07-14 | 2022-10-25 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing milled hot melt adhesive and preparation method thereof |
| CN117467125A (en) * | 2023-12-28 | 2024-01-30 | 河南源宏高分子新材料有限公司 | Polyester material for ageing-resistant film and preparation method thereof |
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| US4907636A (en) * | 1989-01-09 | 1990-03-13 | Newell Co. | Decorative window shade |
| CN101200534A (en) * | 2006-12-13 | 2008-06-18 | 东丽纤维研究所（中国）有限公司 | Polyesters and preparation method thereof |
| CN103539926A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for producing titanium polyester |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4907636A (en) * | 1989-01-09 | 1990-03-13 | Newell Co. | Decorative window shade |
| CN101200534A (en) * | 2006-12-13 | 2008-06-18 | 东丽纤维研究所（中国）有限公司 | Polyesters and preparation method thereof |
| CN103539926A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for producing titanium polyester |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679709A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Polyester for heat shrinkable film and preparation method thereof |
| CN110790907A (en) * | 2019-11-18 | 2020-02-14 | 扬州普立特科技发展有限公司 | Production equipment and process flow of full-continuous PETG |
| CN114426661A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Polyester for high-antistatic heat-shrinkable film and preparation method thereof |
| CN115232293A (en) * | 2022-07-14 | 2022-10-25 | 天津华新盈聚酯材料科技有限公司 | Low-melting-point polyester chip for producing milled hot melt adhesive and preparation method thereof |
| CN117467125A (en) * | 2023-12-28 | 2024-01-30 | 河南源宏高分子新材料有限公司 | Polyester material for ageing-resistant film and preparation method thereof |
| CN117467125B (en) * | 2023-12-28 | 2024-03-08 | 河南源宏高分子新材料有限公司 | Polyester material for ageing-resistant film and preparation method thereof |
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Denomination of invention: A Method for Making Polyester Slices for Heat Shrinkable Film Effective date of registration: 20230710 Granted publication date: 20191112 Pledgee: Industrial and Commercial Bank of China Limited Chaohu sub branch Pledgor: ANHUI WANWEI UPDATED HIGH-TECH MATERIAL INDUSTRY Co.,Ltd. Registration number: Y2023980047850 |
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