CN112442163B - Preparation method of high-molecular polyester antistatic agent - Google Patents
Preparation method of high-molecular polyester antistatic agent Download PDFInfo
- Publication number
- CN112442163B CN112442163B CN202011358650.5A CN202011358650A CN112442163B CN 112442163 B CN112442163 B CN 112442163B CN 202011358650 A CN202011358650 A CN 202011358650A CN 112442163 B CN112442163 B CN 112442163B
- Authority
- CN
- China
- Prior art keywords
- parts
- antistatic agent
- preparation
- reacting
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the field of chemical industry, in particular to a preparation method of a high-molecular terylene antistatic agent; the invention prepares a salt-containing dibasic acid, then the dibasic acid reacts with sulfonic group modified polyether diol to generate polyether ester macromolecules containing metal ions, and then the polyether ester macromolecules react with diisocyanate to carry out chain extension reaction to prepare the macromolecular antistatic agent with a benzene ring structure, and the antistatic agent can improve the antistatic property by means of the double conductive action of polyether ester and metal ions; the sulfonic group modified polyether diol contains sulfonic acid groups, so that the antistatic effect of the polyether diol can be further enhanced; the polyether ester macromolecule is a block polymer containing metal salt, has good antistatic effect as an antistatic agent, has good durability, heat resistance and washing stability, and has good compatibility and processability with polyester materials.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method of a high-molecular polyester antistatic agent.
Background
When polymers are rubbed, the generated static electricity is not easy to release due to high resistance of the polymers, and static voltage is formed along with accumulation of static electricity, so that high polymer products are easy to adsorb dust, the surface performance and the transparency of the products are influenced, and the service performance and the processing performance of the products are also influenced. Moreover, when corona discharge or spark discharge is caused by static electricity, if flammable and explosive substances exist in the surrounding environment, fire or explosion can be caused, and a serious accident can be caused.
CN1011978B is an antistatic agent comprising as a main component a cationic and/or amphoteric water-soluble or water-dispersible thermally reactive blocked urethane prepolymer having at least one cationic group and/or at least one amphoteric group in the molecule and having an isocyanate group blocked with a thermally dissociable blocking agent. The antistatic agent can be used for various materials and can provide these materials with antistatic properties and water resistance which can be maintained for a long period of time.
CN111205509A relates to an antistatic agent. The antistatic agent is prepared from tetrabutyl titanate and pentaerythritol stearate, wherein the weight ratio of tetrabutyl titanate to pentaerythritol stearate is (1-4) to 1. The antistatic agent has excellent antistatic performance, good compatibility with resin, compatibility with other additives, low raw material cost and simple preparation method.
CN109096992A discloses an antistatic agent, which comprises 3-10 parts by weight of quaternary ammonium salt cationic surfactant, 5-20 parts by weight of isopropanol, 15-35 parts by weight of butanone, 20-40 parts by weight of ethyl acetate and 100 parts by weight of pure water. The antistatic effect of the invention is superior to that of the common antistatic agent in the market, and the product produced by the invention has uniform and stable resistance value, can reduce the rejection rate of terminal products, and obviously improves the product performance and economic benefit.
Polyester is the most common textile fiber raw material and is used in a large amount on a plurality of special fabrics, but most of the antistatic agents prepared by the invention and the prior art are micromolecular antistatic agents, the antistatic effect can be exerted only under certain humidity, the migration is easy to occur, and the antistatic effect is greatly reduced after the loss.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a high-molecular polyester antistatic agent.
A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
adding 29.2-43.8 parts of adipic acid and 8.1-12.3 parts of metal oxide into 80-120 parts of acetone according to the mass parts, controlling the temperature to be 30-45 ℃, carrying out reflux reaction for 40-120min, filtering after completion, washing and drying to obtain salt-containing dibasic acid; uniformly mixing the obtained salt-containing dibasic acid with 220-2000 parts of sulfonic acid group modified polyether glycol, adding 0.5-1.6 parts of catalyst, heating to 130-160 ℃ under the protection of nitrogen, reacting at constant temperature for 4-8h, adding 18.2-22.8 parts of phenyl-containing polyisocyanate and 0.2-0.6 part of antioxidant, stirring and uniformly mixing, controlling the temperature to 150-180 ℃ for reaction for 120-60 min, then reacting at reduced pressure for 30-60min, discharging after the reaction is finished, cooling to room temperature, crushing the materials, washing in a water bath at 60-80 ℃ for 30-60min, filtering, and drying to obtain the polymer terylene antistatic agent.
The preparation method of the sulfonic group modified polyether diol comprises the following steps:
according to the mass parts, 24.6-32.4 parts of 5-sulfoisophthalic acid, 200-2000 parts of polyether glycol and 0.8-2.6 parts of methane sulfonic acid are added into a dry reaction kettle, stirred and mixed uniformly under the protection of nitrogen, then heated to 110-130 ℃, stirred and reacted for 1-5 hours, then added with 1.2-3.2 parts of sodium carbonate, stirred and reacted for 30-60 minutes, then the product is added into ethanol for precipitation, stirred for 10-20 minutes, filtered, washed and dried, and the sulfonic group modified polyether glycol is obtained.
The molecular weight of the polyether diol is 1000-10000.
The metal oxide is zinc oxide or copper oxide or calcium oxide.
The catalyst is magnesium acetate or calcium acetate.
The antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether or tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or trioctyl phosphite.
The preparation method of the phenyl-containing polyisocyanate comprises the following steps: according to the weight portion of the components,
1) adding 15-30 parts of 4,4' -diphenylmethane diisocyanate and 20-60 parts of acetone into a closed reaction kettle, keeping the temperature at 25-55 ℃, stirring and dispersing for 10-30min, slowly dropwise adding 5-10 parts of aminoethyl aminopropyl polydimethylsiloxane, reacting for 1-3h after dropwise adding is completed within 0.5-1.5h, then adding 1-5 parts of 4-hydroxystyrene and 1-5 parts of hydroxyethyl acrylate, keeping the temperature at 45-55 ℃ for reacting for 2-4h, and distilling under reduced pressure at 60 ℃ after the reaction is completed to obtain an isocyanate intermediate containing phenyl;
2) adding 10-30 parts of the phenyl-containing isocyanate intermediate obtained in the step 1) and 30-50 parts of dimethylbenzene and 5-15 parts of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.01-0.05 part of chloroplatinic acid, heating to 70-90 ℃, reacting for 8-24h, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
The molecular weight of the hydrogen-containing silicone oil is 1000-1500.
The hydrogen content of the hydrogen-containing silicone oil is 1-3%.
Wherein a part of the reaction formula in the preparation method of the phenyl-containing polyisocyanate can be represented by the following formula:
1) isocyanate in 4,4' -diphenylmethane diisocyanate reacts with active N-H of aminoethyl aminopropyl polydimethylsiloxane, and isocyanate reacts with partial-OH in hydroxyethyl acrylate and 4-hydroxystyrene to generate isocyanate intermediate containing phenyl. The equation for its partial reaction is schematically:
2) then, the hydrogen-containing silicone oil and the intermediate undergo hydrosilylation in the presence of chloroplatinic acid, and the intermediate with isocyanate is bonded into the hydrogen-containing silicone oil to obtain the phenyl-containing polyisocyanate of the invention. The equation for its partial reaction is schematically:
according to the preparation method of the high-molecular polyester antistatic agent, the salt-containing dibasic acid is prepared, then the dibasic acid reacts with the sulfonic group modified polyether diol to generate polyether ester macromolecules containing metal ions, and then the polyether ester macromolecules react with polyisocyanate chain extension to prepare the high-molecular antistatic agent with a benzene ring structure, wherein the antistatic agent can improve the antistatic property by means of the double conductive action of the polyether ester and the metal ions; the sulfonic group modified polyether diol contains sulfonic acid groups, so that the antistatic effect of the polyether diol can be further enhanced; the polyether ester macromolecule is a block polymer containing metal salt, has good antistatic effect as an antistatic agent, has good durability, heat resistance and washing stability, and has good compatibility and processability with polyester materials; in the structure of the high-molecular polyester antistatic agent, due to the chain extension effect of the polyisocyanate chain extender, a shell-core structure with the chain extender as a core and polyether ester molecules as a shell is formed, so that the compatibility is improved and the shell-core structure can be used as a charge channel.
Drawings
FIG. 1 is a Fourier infrared spectrum of the product polyisocyanate containing phenyl groups prepared in example 2:
at 1500/1449cm-1An absorption peak of benzene ring is present nearby, and is 2966cm-1The expansion and contraction absorption peak of the hydrocarbon exists nearby and is 1684cm-1The absorption peak of the amide in the vicinity of the carbonyl group is 1381cm-1An expansion absorption peak of a carbon-nitrogen single bond exists nearby, which indicates that 4,4' -diphenylmethane diisocyanate participates in the reaction; at 1085/1026/808cm-1An antisymmetric stretching/symmetric stretching absorption peak of a silicon-oxygen bond exists nearby, and is at 624cm-1A stretching absorption peak of silicon-carbon bond exists nearby, which indicates that hydrogen-containing silicone oil participates in the reaction; at 927cm-1An absorption peak of a silicon nitrogen bond of 3388cm is present in the vicinity thereof-1A stretching absorption peak of a nitrogen-hydrogen bond exists nearby, so that the aminoethyl aminopropyl polydimethylsiloxane participates in the reaction; at 1179cm-1The antisymmetric telescopic absorption peak of the ester carbon-oxygen single bond exists nearby and is 1732cm-1A telescopic absorption peak of ester carbonyl exists nearby, and the 4-hydroxystyrene participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
the antistatic agent/polyester prepared according to each example is mixed with polyester at a mass ratio of 5%, mixed in an open mill, pressed into sheets by a vulcanizer, tested by a YG321 type material specific resistance tester, and the test conditions are as follows: specific resistance values were tested at 25 ℃ and 40% humidity. The electrostatic half-life of the blended material was tested using model DWJ-81 electrostatic potentiometers from Shanghai electronics. And (3) testing conditions are as follows: the temperature is 20 +/-1 ℃, and the relative humidity is 65 +/-5%.
Example 1
A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
adding 29.2g of adipic acid and 8.1g of metal oxide into 80g of acetone, controlling the temperature at 30 ℃, carrying out reflux reaction for 40min, filtering after completion, washing and drying to obtain salt-containing dibasic acid; uniformly mixing the obtained salt-containing dibasic acid with 220g of sulfonic group modified polyether glycol, adding 0.5g of catalyst, heating to 130 ℃ under the protection of nitrogen, reacting at a constant temperature for 4h, adding 18.2g of phenyl-containing polyisocyanate and 0.2g of antioxidant, stirring, uniformly mixing, controlling the temperature to 150 ℃, reacting for 120min, then reacting at a reduced pressure for 30min, discharging after the reaction is finished, cooling to room temperature, crushing the material, washing for 30min in a water bath at 60 ℃, filtering, and drying to obtain the high-molecular polyester antistatic agent.
The preparation method of the sulfonic group modified polyether diol comprises the following steps:
adding 24.6g of 5-sulfoisophthalic acid, 200g of polyether glycol and 0.8g of methanesulfonic acid into a dry reaction kettle, stirring and mixing uniformly under the protection of nitrogen, heating to 110 ℃, stirring for reaction for 1h, adding 1.2g of sodium carbonate, stirring for reaction for 30min, adding the product into ethanol for precipitation, stirring for 10min, filtering, washing and drying to obtain the sulfonic group modified polyether glycol.
The molecular weight of the polyether diol is 1000.
The metal oxide is zinc oxide.
The catalyst is magnesium acetate.
The antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether.
The preparation method of the phenyl-containing polyisocyanate comprises the following steps:
1) adding 30g of 4,4' -diphenylmethane diisocyanate and 60g of acetone into a closed reaction kettle, keeping the temperature at 25 ℃, stirring and dispersing for 30min, slowly dropwise adding 10g of aminoethyl aminopropyl polydimethylsiloxane, reacting for 1h after 0.5h of dropwise addition is finished, then adding 1g of 4-hydroxystyrene and 5g of hydroxyethyl acrylate, keeping the temperature at 55 ℃ for reacting for 2h, and carrying out reduced pressure distillation at 60 ℃ after the reaction is finished to obtain an isocyanate intermediate containing phenyl;
2) adding 10g of the phenyl-containing isocyanate intermediate obtained in the step 1) and 30g of dimethylbenzene and 15g of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.05g of chloroplatinic acid, heating to 70 ℃, reacting for 24 hours, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
The molecular weight of the hydrogen-containing silicone oil is 1000.
The hydrogen content of the hydrogen-containing silicone oil is 1 percent.
Example 2
A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
adding 36.4g of adipic acid and 10.2g of metal oxide into 100g of acetone, controlling the temperature to be 35 ℃, carrying out reflux reaction for 80min, filtering after completion, washing and drying to obtain salt-containing dibasic acid; uniformly mixing the obtained salt-containing dibasic acid with 1000g of sulfonic group modified polyether glycol, adding 1.2g of catalyst, heating to 140 ℃ under the protection of nitrogen, reacting at a constant temperature for 6h, adding 20.4g of phenyl-containing polyisocyanate and 0.4g of antioxidant, stirring, uniformly mixing, controlling the temperature to 160 ℃, reacting for 150min, then reacting at a reduced pressure for 40min, discharging after the reaction is finished, cooling to room temperature, crushing the material, washing for 40min in 70 ℃ water bath, filtering, and drying to obtain the high-molecular polyester antistatic agent.
The preparation method of the sulfonic group modified polyether diol comprises the following steps:
adding 28.6g of 5-sulfoisophthalic acid, 1000g of polyether glycol and 1.6g of methanesulfonic acid into a dry reaction kettle, stirring and mixing uniformly under the protection of nitrogen, heating to 120 ℃, stirring for reaction for 3 hours, adding 2.2g of sodium carbonate, stirring for reaction for 40 minutes, adding the product into ethanol for precipitation, stirring for 15 minutes, filtering, washing and drying to obtain the sulfonic group modified polyether glycol.
The molecular weight of the polyether diol is 5000.
The metal oxide is copper oxide.
The catalyst is calcium acetate.
The antioxidant is tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
The preparation method of the phenyl-containing polyisocyanate comprises the following steps:
1) adding 15g of 4,4' -diphenylmethane diisocyanate and 20g of acetone into a closed reaction kettle, keeping the temperature at 55 ℃, stirring and dispersing for 10min, slowly dropwise adding 5g of aminoethyl aminopropyl polydimethylsiloxane, reacting for 1h after 1.5h of dropwise addition is finished, then adding 5g of 4-hydroxystyrene and 1g of hydroxyethyl acrylate, keeping the temperature at 45 ℃ for reacting for 4h, and carrying out reduced pressure distillation at 60 ℃ after the reaction is finished to obtain an isocyanate intermediate containing phenyl;
2) adding 30g of the phenyl-containing isocyanate intermediate obtained in the step 1) and 50g of dimethylbenzene and 5g of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.01g of chloroplatinic acid, heating to 90 ℃, reacting for 8 hours, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
The molecular weight of the hydrogen-containing silicone oil is 1500.
The hydrogen content of the hydrogen-containing silicone oil is 3%.
Example 3
A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
adding 43.8g of adipic acid and 12.3g of metal oxide into 120g of acetone, controlling the temperature at 45 ℃, carrying out reflux reaction for 120min, filtering after completion, washing and drying to obtain salt-containing dibasic acid; uniformly mixing the obtained salt-containing dibasic acid with 2000g of sulfonic group modified polyether glycol, adding 1.6g of catalyst, heating to 160 ℃ under the protection of nitrogen, reacting at a constant temperature for 8 hours, adding 22.8g of phenyl-containing polyisocyanate and 0.6g of antioxidant, stirring, uniformly mixing, controlling the temperature to 180 ℃, reacting for 180min, then reacting at reduced pressure for 60min, discharging after the reaction is finished, cooling to room temperature, crushing the material, washing for 60min in a water bath at 80 ℃, filtering, and drying to obtain the high-molecular polyester antistatic agent.
The preparation method of the sulfonic group modified polyether diol comprises the following steps:
adding 32.4g of 5-sulfoisophthalic acid, 2000g of polyether glycol and 2.6g of methanesulfonic acid into a dry reaction kettle, stirring and mixing uniformly under the protection of nitrogen, heating to 130 ℃, stirring for reaction for 5 hours, adding 3.2g of sodium carbonate, stirring for reaction for 60 minutes, adding the product into ethanol for precipitation, stirring for 20 minutes, filtering, washing, and drying to obtain the sulfonic group modified polyether glycol.
The molecular weight of the polyether diol is 10000.
The metal oxide is calcium oxide.
The catalyst is calcium acetate.
The antioxidant is trioctyl phosphite.
The preparation method of the phenyl-containing polyisocyanate comprises the following steps:
1) adding 20g of 4,4' -diphenylmethane diisocyanate and 40g of acetone into a closed reaction kettle, keeping the temperature at 40 ℃, stirring and dispersing for 20min, slowly dropwise adding 7g of aminoethyl aminopropyl polydimethylsiloxane, reacting for 2h after 1h of dropwise addition is finished, then adding 3g of 4-hydroxystyrene and 4g of hydroxyethyl acrylate, keeping the temperature at 50 ℃ for reacting for 4h, and carrying out reduced pressure distillation at 60 ℃ after the reaction is finished to obtain an isocyanate intermediate containing phenyl;
2) adding 20g of the phenyl-containing isocyanate intermediate obtained in the step 1) and 40g of dimethylbenzene and 9g of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.03g of chloroplatinic acid, heating to 80 ℃, reacting for 14 hours, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
The molecular weight of the hydrogen-containing silicone oil is 1200.
The hydrogen content of the hydrogen-containing silicone oil is 2 percent.
The performance results of the polyester products corresponding to the antistatic agents prepared in the above examples are shown in the following table:
| static half life(s) | Specific resistance value (omega/cm) | |
| Pure polyester fibre | -- | 3.47×1016 |
| Example 1 | 0.92 | 8.62×109 |
| Example 2 | 0.83 | 7.57×109 |
| Example 3 | 0.78 | 7.21×109 |
Comparative example 1
A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
uniformly mixing 29.2g of adipic acid and 220g of sulfonic group modified polyether glycol, adding 0.5g of catalyst, heating to 130 ℃ under the protection of nitrogen, reacting at a constant temperature for 4 hours, adding 18.2g of phenyl-containing polyisocyanate and 0.2g of antioxidant, stirring, uniformly mixing, controlling the temperature to 150 ℃, reacting for 120min, then reacting at a reduced pressure for 30min, discharging after the reaction is finished, cooling to room temperature, crushing the material, washing for 30min in a water bath at 60 ℃, filtering, and drying to obtain the high-molecular polyester antistatic agent.
The preparation method of the sulfonic group modified polyether diol comprises the following steps:
adding 24.6g of 5-sulfoisophthalic acid, 200g of polyether glycol and 0.8g of methanesulfonic acid into a dry reaction kettle, stirring and mixing uniformly under the protection of nitrogen, heating to 110 ℃, stirring for reaction for 1h, adding 1.2g of sodium carbonate, stirring for reaction for 30min, adding the product into ethanol for precipitation, stirring for 10min, filtering, washing and drying to obtain the sulfonic group modified polyether glycol.
The molecular weight of the polyether diol is 1000.
The catalyst is magnesium acetate.
The antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether.
The preparation method of the phenyl-containing polyisocyanate comprises the following steps:
1) adding 30g of 4,4' -diphenylmethane diisocyanate and 60g of acetone into a closed reaction kettle, keeping the temperature at 25 ℃, stirring and dispersing for 30min, slowly dropwise adding 10g of aminoethyl aminopropyl polydimethylsiloxane, reacting for 1h after 0.5h of dropwise addition is finished, then adding 1g of 4-hydroxystyrene and 5g of hydroxyethyl acrylate, keeping the temperature at 55 ℃ for reacting for 2h, and carrying out reduced pressure distillation at 60 ℃ after the reaction is finished to obtain an isocyanate intermediate containing phenyl;
2) adding 10g of the phenyl-containing isocyanate intermediate obtained in the step 1) and 30g of dimethylbenzene and 15g of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.05g of chloroplatinic acid, heating to 70 ℃, reacting for 24 hours, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
The molecular weight of the hydrogen-containing silicone oil is 1000.
The hydrogen content of the hydrogen-containing silicone oil is 1 percent.
Comparative example 2
A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
adding 29.2g of adipic acid and 8.1g of metal oxide into 80g of acetone, controlling the temperature at 30 ℃, carrying out reflux reaction for 40min, filtering after completion, washing and drying to obtain salt-containing dibasic acid; uniformly mixing the obtained salt-containing dibasic acid with 220g of polyether glycol, adding 0.5g of catalyst, heating to 130 ℃ under the protection of nitrogen, reacting at a constant temperature for 4 hours, adding 18.2g of phenyl-containing polyisocyanate and 0.2g of antioxidant, stirring, uniformly mixing, controlling the temperature to 150 ℃, reacting for 120 minutes, then reacting at a reduced pressure for 30 minutes, discharging after the reaction is finished, cooling to room temperature, crushing the material, washing for 30 minutes in a water bath at 60 ℃, filtering, and drying to obtain the high-molecular polyester antistatic agent.
The molecular weight of the polyether diol is 1000.
The metal oxide is zinc oxide.
The catalyst is magnesium acetate.
The antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether.
The preparation method of the phenyl-containing polyisocyanate comprises the following steps:
1) adding 30g of 4,4' -diphenylmethane diisocyanate and 60g of acetone into a closed reaction kettle, keeping the temperature at 25 ℃, stirring and dispersing for 30min, slowly dropwise adding 10g of aminoethyl aminopropyl polydimethylsiloxane, reacting for 1h after 0.5h of dropwise addition is finished, then adding 1g of 4-hydroxystyrene and 5g of hydroxyethyl acrylate, keeping the temperature at 55 ℃ for reacting for 2h, and carrying out reduced pressure distillation at 60 ℃ after the reaction is finished to obtain an isocyanate intermediate containing phenyl;
2) adding 10g of the phenyl-containing isocyanate intermediate obtained in the step 1) and 30g of dimethylbenzene and 15g of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.05g of chloroplatinic acid, heating to 70 ℃, reacting for 24 hours, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
The molecular weight of the hydrogen-containing silicone oil is 1000.
The hydrogen content of the hydrogen-containing silicone oil is 1 percent.
Comparative example 3
A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
adding 29.2g of adipic acid and 8.1g of metal oxide into 80g of acetone, controlling the temperature at 30 ℃, carrying out reflux reaction for 40min, filtering after completion, washing and drying to obtain salt-containing dibasic acid; and uniformly mixing the obtained salt-containing dibasic acid with 220g of sulfonic group modified polyether glycol, adding 0.5g of catalyst, heating to 130 ℃ under the protection of nitrogen, reacting at a constant temperature for 4 hours, discharging after the reaction is finished, cooling to room temperature, crushing the material, washing in a water bath at 60 ℃ for 30min, filtering, and drying to obtain the high-molecular polyester antistatic agent.
The preparation method of the sulfonic group modified polyether diol comprises the following steps:
adding 24.6g of 5-sulfoisophthalic acid, 200g of polyether glycol and 0.8g of methanesulfonic acid into a dry reaction kettle, stirring and mixing uniformly under the protection of nitrogen, heating to 110 ℃, stirring for reaction for 1h, adding 1.2g of sodium carbonate, stirring for reaction for 30min, adding the product into ethanol for precipitation, stirring for 10min, filtering, washing and drying to obtain the sulfonic group modified polyether glycol.
The molecular weight of the polyether diol is 1000.
The metal oxide is zinc oxide.
The catalyst is magnesium acetate.
The antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether.
The preparation method of the phenyl-containing polyisocyanate comprises the following steps:
1) adding 30g of 4,4' -diphenylmethane diisocyanate and 60g of acetone into a closed reaction kettle, keeping the temperature at 25 ℃, stirring and dispersing for 30min, slowly dropwise adding 10g of aminoethyl aminopropyl polydimethylsiloxane, reacting for 1h after 0.5h of dropwise addition is finished, then adding 1g of 4-hydroxystyrene and 5g of hydroxyethyl acrylate, keeping the temperature at 55 ℃ for reacting for 2h, and carrying out reduced pressure distillation at 60 ℃ after the reaction is finished to obtain an isocyanate intermediate containing phenyl;
2) adding 10g of the phenyl-containing isocyanate intermediate obtained in the step 1) and 30g of dimethylbenzene and 15g of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.05g of chloroplatinic acid, heating to 70 ℃, reacting for 24 hours, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
The molecular weight of the hydrogen-containing silicone oil is 1000.
The hydrogen content of the hydrogen-containing silicone oil is 1 percent.
The performance results of the polyester products corresponding to the antistatic agents prepared by the above comparative examples are shown in the following table:
| static half life(s) | Specific resistance value (omega/cm) | |
| Comparative example 1 | 1.82 | 7.15×1010 |
| Comparative example 2 | 1.76 | 6.47×1010 |
| Comparative example 3 | 1.12 | 9.81×109 |
Claims (8)
1. A preparation method of a polymer terylene antistatic agent comprises the following specific scheme:
adding 29.2-43.8 parts of adipic acid and 8.1-12.3 parts of metal oxide into 80-120 parts of acetone according to the mass parts, controlling the temperature to be 30-45 ℃, carrying out reflux reaction for 40-120min, filtering after completion, washing and drying to obtain salt-containing dibasic acid; uniformly mixing the obtained salt-containing dibasic acid with 220-2000 parts of sulfonic acid group modified polyether glycol, adding 0.5-1.6 parts of catalyst, heating to 130-160 ℃ under the protection of nitrogen, reacting at constant temperature for 4-8h, adding 18.2-22.8 parts of phenyl-containing polyisocyanate and 0.2-0.6 part of antioxidant, stirring and uniformly mixing, controlling the temperature to 150-180 ℃ for reaction for 120-60 min, then reacting at reduced pressure for 30-60min, discharging after the reaction is finished, cooling to room temperature, crushing the material, washing in a water bath at 60-80 ℃ for 30-60min, filtering, and drying to obtain the polymer terylene antistatic agent;
the preparation method of the phenyl-containing polyisocyanate comprises the following steps: according to the weight portion of the components,
1) adding 15-30 parts of 4,4' -diphenylmethane diisocyanate and 20-60 parts of acetone into a closed reaction kettle, keeping the temperature at 25-55 ℃, stirring and dispersing for 10-30min, slowly dropwise adding 5-10 parts of aminoethyl aminopropyl polydimethylsiloxane, reacting for 1-3h after dropwise adding is completed within 0.5-1.5h, then adding 1-5 parts of 4-hydroxystyrene and 1-5 parts of hydroxyethyl acrylate, keeping the temperature at 45-55 ℃ for reacting for 2-4h, and distilling under reduced pressure at 60 ℃ after the reaction is completed to obtain an isocyanate intermediate containing phenyl;
2) adding 10-30 parts of the phenyl-containing isocyanate intermediate obtained in the step 1) and 30-50 parts of dimethylbenzene and 5-15 parts of hydrogen-containing silicone oil into a closed reaction kettle, adding 0.01-0.05 part of chloroplatinic acid, heating to 70-90 ℃, reacting for 8-24h, then carrying out reduced pressure distillation at 130 ℃, and filtering to obtain the phenyl-containing polyisocyanate.
2. The preparation method of the polymer polyester antistatic agent according to claim 1, characterized in that: the preparation method of the sulfonic group modified polyether diol comprises the following steps:
according to the mass parts, 24.6-32.4 parts of 5-sulfoisophthalic acid, 200-2000 parts of polyether glycol and 0.8-2.6 parts of methane sulfonic acid are added into a dry reaction kettle, stirred and mixed uniformly under the protection of nitrogen, then heated to 110-130 ℃, stirred and reacted for 1-5 hours, then added with 1.2-3.2 parts of sodium carbonate, stirred and reacted for 30-60 minutes, then the product is added into ethanol for precipitation, stirred for 10-20 minutes, filtered, washed and dried, and the sulfonic group modified polyether glycol is obtained.
3. The preparation method of the polymer polyester antistatic agent according to claim 2, characterized in that: the molecular weight of the polyether diol is 1000-10000.
4. The preparation method of the polymer polyester antistatic agent according to claim 1, characterized in that: the metal oxide is zinc oxide or copper oxide or calcium oxide.
5. The preparation method of the polymer polyester antistatic agent according to claim 1, characterized in that: the catalyst is magnesium acetate or calcium acetate.
6. The preparation method of the polymer polyester antistatic agent according to claim 1, characterized in that: the antioxidant is bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether or tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester or trioctyl phosphite.
7. The preparation method of the polymer polyester antistatic agent according to claim 6, characterized in that: the molecular weight of the hydrogen-containing silicone oil is 1000-1500.
8. The preparation method of the polymer polyester antistatic agent according to claim 7, characterized in that: the hydrogen content of the hydrogen-containing silicone oil is 1-3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011358650.5A CN112442163B (en) | 2020-11-27 | 2020-11-27 | Preparation method of high-molecular polyester antistatic agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011358650.5A CN112442163B (en) | 2020-11-27 | 2020-11-27 | Preparation method of high-molecular polyester antistatic agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112442163A CN112442163A (en) | 2021-03-05 |
| CN112442163B true CN112442163B (en) | 2021-11-26 |
Family
ID=74737821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011358650.5A Active CN112442163B (en) | 2020-11-27 | 2020-11-27 | Preparation method of high-molecular polyester antistatic agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112442163B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116217879B (en) * | 2023-05-06 | 2023-07-28 | 江苏富淼科技股份有限公司 | Cationic antistatic agent, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778445A (en) * | 2016-05-12 | 2016-07-20 | 华南师范大学 | High molecular antistatic agent and preparation method thereof |
| JP2019189545A (en) * | 2018-04-20 | 2019-10-31 | 三菱マテリアル電子化成株式会社 | Reactive fluorine-containing sulfonylimide and polymer thereof, and antistatic agent containing the same |
| CN111893767A (en) * | 2020-07-29 | 2020-11-06 | 日华化学（中国）有限公司 | Durable antistatic agent for polyester fabric and preparation method of polyester antistatic fabric |
-
2020
- 2020-11-27 CN CN202011358650.5A patent/CN112442163B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778445A (en) * | 2016-05-12 | 2016-07-20 | 华南师范大学 | High molecular antistatic agent and preparation method thereof |
| JP2019189545A (en) * | 2018-04-20 | 2019-10-31 | 三菱マテリアル電子化成株式会社 | Reactive fluorine-containing sulfonylimide and polymer thereof, and antistatic agent containing the same |
| CN111893767A (en) * | 2020-07-29 | 2020-11-06 | 日华化学（中国）有限公司 | Durable antistatic agent for polyester fabric and preparation method of polyester antistatic fabric |
Non-Patent Citations (1)
| Title |
|---|
| 浅谈高分子材料用抗静电剂;胡树，黎鹏，郭辉;《塑料助剂》;20180226;第46-51页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112442163A (en) | 2021-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106279619B (en) | One kind being based on hydrogen bond action thermal drivers selfreparing method for producing elastomers | |
| CN110591542A (en) | Disulfide bond and hydrogen bond containing dual self-repairing polyurethane coating for invisible car cover and preparation method thereof | |
| CN112442163B (en) | Preparation method of high-molecular polyester antistatic agent | |
| WO2022147914A1 (en) | Solvent-free polyurethane resin for high-flame-retardancy automobile leather, and preparation method therefor | |
| CN113214450A (en) | Wear-resistant self-repairing type polyurethane composite coating agent based on shape memory and preparation method thereof | |
| CN111607055B (en) | High molecular weight polyurethane based on dynamic reversible covalent bond and preparation method and application thereof | |
| CN109456459A (en) | A method of raising aqueous polyurethane is water-fast or solvent resistance | |
| Chen et al. | Polyurethane cationomers. I. Structure‐property relationships | |
| CN110358039B (en) | Preparation method of self-coloring polyurethane based on zwitterion, product and application thereof | |
| CN109957031A (en) | The reversible chain extender of cellulose fibre and its chain extender composition for preparing and include it | |
| JP3980554B2 (en) | Spandex with quaternary amine additives | |
| CN113861051A (en) | Polyurethane material and preparation, recovery and regeneration method thereof | |
| CN113105608A (en) | Self-healing hyperbranched polyurethane with high mechanical strength and preparation method and application thereof | |
| Kapatel et al. | Flame retardant waterborne polyurethanes: Synthesis, characterization, and evaluation of different properties | |
| CN107056840B (en) | A kind of preparation method of response type nitrogen phosphorus fire retardant | |
| CN113755966B (en) | Preparation method of PBT (polybutylene terephthalate) slice for memory-fiber-imitated fiber | |
| CN111777887A (en) | Flame-retardant heat-resistant waterborne polyurethane coating and preparation method thereof | |
| CN113622050B (en) | Preparation method of high-resilience chlorine-resistant spandex fiber and application of high-resilience chlorine-resistant spandex fiber in diaper | |
| CN115785383A (en) | Preparation method of self-repairing polyurethane containing DA bond and acylhydrazone bond double cross-linking | |
| CN110951064B (en) | Phthalocyanine metal salt modified polyurethane elastomer and preparation method thereof | |
| CN110528293B (en) | Flame-retardant antifouling synthetic leather and preparation method thereof | |
| CN114702891A (en) | Flame-retardant hydrophobic coating for electric energy metering box and preparation method thereof | |
| CN111501127B (en) | Carbon dioxide-based polyurethane fiber and preparation method thereof | |
| CN114854004B (en) | Nonionic type double-amino hydrophilic chain extender, preparation method thereof and preparation method of nonionic type aqueous polyurea | |
| JP3712092B2 (en) | Polyurethane elastic fiber and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211102 Address after: 201614 floor 3, building 10, No. 488, Guanghua Road, Xiaokunshan Town, Songjiang District, Shanghai Applicant after: Shanghai Kaifei Clothing Co.,Ltd. Address before: Floor 8, building 5, biological industry Incubation Park, No.60 Keyuan Avenue, high tech Development Zone, Nanning, Guangxi 530000 Applicant before: Guangxi mandili Biotechnology Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |