CN111057351A - PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof - Google Patents
PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof Download PDFInfo
- Publication number
- CN111057351A CN111057351A CN201911210978.XA CN201911210978A CN111057351A CN 111057351 A CN111057351 A CN 111057351A CN 201911210978 A CN201911210978 A CN 201911210978A CN 111057351 A CN111057351 A CN 111057351A
- Authority
- CN
- China
- Prior art keywords
- bis
- pbt
- packaging bag
- environment
- trimethoxysilylpropyl
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Wrappers (AREA)
Abstract
The invention discloses a PBT environment-friendly packaging bag which is characterized by being prepared from the following raw materials in parts by weight: 65-75 parts of PBT resin, 10-20 parts of chloromethyl aza-silazane-ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 3-5 parts of alginic acid, 4-8 parts of attapulgite clay powder, 0.3-0.5 part of antioxidant and 0.2-0.4 part of lubricant. The invention also discloses a production process of the PBT environment-friendly packaging bag. The PBT environment-friendly packaging bag disclosed by the invention is good in environmental protection, water resistance and weather resistance, mechanical property and heat resistance, impact strength and comprehensive performance and long in service life.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PBT (polybutylene terephthalate) environment-friendly packaging bag and a production process thereof.
Background
In recent years, with the improvement of the living standard of people and the progress of science and technology, consumers put forward various new requirements on packaging materials, and especially the high performance, multifunction and environmental protection performance of the packaging materials are concerned. Therefore, development of a packaging material having excellent properties is indispensable.
The packaging bag is a common packaging material, is also commonly called as a handbag, is a bag used for packaging various articles, facilitates the transportation and easy storage of goods in the production flow process, and is widely applied to the packaging of food, clothes, medicines, books and periodicals, gifts, artworks and the like. The packaging bag made of plastic becomes the mainstream development direction of the packaging bag industry due to the advantages of light weight, thinness, impermeability, high strength and low cost, and brings great convenience to the daily life of people. However, the plastic packaging bags in the prior art have the defects of low tensile strength and elongation at break, easy cracking and damage caused by impact in the packaging and transportation process, and serious resource waste, environmental pollution and poor water vapor permeability caused by compounding the film and the base material (copper sheet paper or paperboard) by using an adhesive with toxic and harmful components such as benzene, toluene, methanol, formaldehyde, styrene, dichloromethane, carbon tetrachloride, ethylene diamine and the like.
Polybutylene terephthalate resin (hereinafter, PBT resin) belongs to a polyester series, is a milky translucent to opaque crystalline thermoplastic polyester material prepared by condensing 1, 4-butanediol with terephthalic acid or terephthalic acid ester and by a mixing process, has excellent mechanical properties, outstanding chemical reagent resistance, abrasion resistance, heat resistance and fatigue resistance, excellent electrical properties, better flexibility, wind resistance and water resistance, does not generate toxic and harmful substances after waste combustion treatment, and is expected to become a good material for an environment-friendly plastic packaging bag.
The Chinese patent with the publication number of CN103862772B discloses a high-performance barrier environment-friendly packaging material for an inner bag of a flexible freight bag and a preparation method thereof, belonging to the technical field of flexible packaging materials. The structure of the adhesive comprises a first polyethylene layer, a first adhesive layer, an ethylene-vinyl alcohol (EVOH) layer, a second adhesive layer and a second polyethylene layer from top to bottom in sequence; the composite film is prepared by adopting a five-layer coextrusion casting method. The high-performance barrier environment-friendly packaging material for the inner bag of the flexible freight bag, prepared by the invention, has good barrier performance, and the packaged goods are not easy to deteriorate, are environment-friendly, and save resources and energy; the film has good film transparency and appearance effect, good thickness deviation and good heat sealing performance; however, the polyethylene-based composite material adopts a multilayer structure design, so that on one hand, the preparation process is complex, the preparation cost is high, on the other hand, in the long-term use process, the delamination phenomenon occurs when the polyethylene-based composite material is dissolved, the performance stability needs to be further improved, and the polyethylene-based composite material has the defect of poor thermal aging property.
Therefore, the development of the PBT environment-friendly packaging bag with comprehensive performance is very necessary, and the PBT environment-friendly packaging bag has very important significance for promoting the development of the packaging bag industry.
Disclosure of Invention
The invention mainly aims to provide the PBT environment-friendly packaging bag and the production process thereof, and the production process is simple, convenient to operate, low in equipment dependence, low in production cost and high in production efficiency; the produced PBT environment-friendly packaging bag has the advantages of good environmental protection, good waterproof performance and weather resistance, good mechanical property and heat resistance, high impact strength, excellent comprehensive performance and long service life.
In order to achieve the purpose, the invention provides a PBT environment-friendly packaging bag which is characterized by being prepared from the following raw materials in parts by weight: 65-75 parts of PBT resin, 10-20 parts of chloromethyl aza-silazane-ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 3-5 parts of alginic acid, 4-8 parts of attapulgite clay powder, 0.3-0.5 part of antioxidant and 0.2-0.4 part of lubricant.
Further, the lubricant is at least one of paraffin and polydimethylsiloxane.
The antioxidant is at least one of tris (2, 4-di-tert-butyl) phenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and dioctadecyl pentaerythritol diphosphite.
Further, the preparation method of the chloromethyl aza-silazane-ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester comprises the following steps:
step S1: adding benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, a catalyst and a high-boiling point solvent into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, then carrying out esterification reaction for 4-6 hours under the conditions of the temperature of 235-245 ℃ and the absolute pressure of 20-80 KPa, ending esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature between 280 ℃ and 300 ℃, stirring and reacting for 15-20h, cooling to room temperature after the reaction is finished, discharging and precipitating in acetone, washing the precipitated product with diethyl ether for 4-8 times, and then removing the diethyl ether by rotary evaporation to obtain benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester;
step S2: chloromethyl aza silatrane and poly benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester prepared in the step S1 are added into N-methyl pyrrolidone to be stirred and reacted for 6 to 8 hours at the temperature of 40 to 60 ℃, then the N-methyl pyrrolidone is removed by rotary evaporation, the product is washed by ethyl ether for 4 to 8 times, and then the ethyl ether is removed by rotary evaporation, thus obtaining the chloromethyl aza silatrane ionized modified poly benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester.
Furthermore, in step S1, the mass ratio of the benzophenone-4, 4' -dicarboxylic acid to the N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine to the catalyst to the high-boiling point solvent is 1:1.75 (0.4-0.6) to (10-15).
Preferably, the catalyst is at least one of tetrabutyl titanate, methyl benzene sulfonic acid and titanium chloride; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
Further, in step S2, the mass ratio of chloromethylsilatrane to polybenophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester to N-methylpyrrolidone is (0.1-0.2):1 (3-5).
The invention also aims to provide a production process of the PBT environment-friendly packaging bag, which is characterized by comprising the following steps:
step D1: uniformly mixing the raw materials to obtain a mixture, adding the mixture into a double-screw extruder for extrusion, performing tape casting to form a film, and slitting the film by using a slitting machine according to the specification of a packaging bag to obtain a bag piece;
step D2: and (5) die-cutting the bag sheet prepared in the step S1, and then conveying the bag sheet to a bag making machine for making bags to obtain the PBT environment-friendly packaging bag.
Further, the extrusion process parameters in D1 are: the temperature of each section of the double-screw extruder is from a charging opening to 185-plus-190 ℃, 195-plus-200 ℃, 205-plus-210 ℃, 215-plus-220 ℃, 225-plus-230 ℃ and 230-plus-235 ℃ in sequence, and the temperature of the head of the extruder is 220-plus-230 ℃.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the PBT environment-friendly packaging bag disclosed by the invention is simple in production process, convenient to operate, low in equipment dependence, low in production cost and high in production efficiency.
(2) The PBT environment-friendly packaging bag disclosed by the invention overcomes the defects that the traditional packaging bag is low in tensile strength and elongation at break, is easy to break and damage when being impacted in the packaging and transporting process, and the film and a base material (copper sheet paper or paperboard) are compounded by using an adhesive with toxic and harmful components such as benzene, toluene, methanol, formaldehyde, styrene, dichloromethane, carbon tetrachloride, ethylenediamine and the like, so that serious resource waste and environmental pollution are easily caused, and the waterproof vapor permeability is poor.
(3) The invention discloses a PBT environment-friendly packaging bag which is prepared by taking PBT resin as a base material and adding chloromethyl heteroazasilane ionization modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, alginic acid, attapulgite clay powder, an antioxidant and a lubricant, firstly, the excellent comprehensive performance of the PBT resin material is kept, the chloromethyl heteroazasilane ionization modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester and the PBT both belong to polyester structures and have good compatibility, the chloromethyl heteroazasilane ionization modified poly-benzophenone-4, 4' -dicarboxylic acid N, the N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester is prepared by firstly performing polycondensation on carboxyl on benzophenone-4, 4' -dicarboxylic acid and hydroxyl on N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine to form ester, then performing ionization reaction on chlorine on chloromethyl aza-silazane and tertiary amino on the obtained polyester molecular chain, introducing a quaternary ammonium salt cation structure, introducing a benzophenone structure on the molecular main chain, facilitating improvement of ultraviolet aging resistance of the material, and effectively improving waterproof performance by synergistic effect with the introduced aza-silazane structure; the introduced ionic structure is easy to form an ionic crosslinking structure with the added alginic acid, so that the comprehensive performance is further improved; the introduced alginic acid has excellent biodegradation function, and the material is easy to post-treat after being discarded; in addition, a methoxy silicon structure is introduced on a side chain of the chloromethyl aza-silazane trialkyl ionized modified poly (benzophenone) -4,4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, which is favorable for improving the compatibility between organic and inorganic components and ensures that the attapulgite clay powder is easier to disperse; the addition of the attapulgite clay powder is beneficial to enhancing and absorbing peculiar smell; all the components have synergistic effect, so that the comprehensive performance is better.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
In the embodiment of the invention, the raw materials are all purchased commercially; the PBT resin is American Tycona 1700A high molecular weight PBT Celanex; the CAS number of the chloromethyl aza-silazane is 42003-39-4; the CAS number of the N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine is 214362-07-9.
Example 1
The PBT environment-friendly packaging bag is characterized by being prepared from the following raw materials in parts by weight: 65 parts of PBT resin, 10 parts of chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 3 parts of alginic acid, 4 parts of attapulgite clay powder, 0.3 part of tris (2, 4-di-tert-butyl) phenyl phosphite and 0.2 part of paraffin.
The preparation method of the chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester comprises the following steps:
step S1: adding 100g of benzophenone-4, 4' -dicarboxylic acid, 175g of N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, 40g of tetrabutyl titanate and 1000g of dimethyl sulfoxide into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, carrying out esterification reaction for 4 hours at 235 ℃ and 20KPa absolute pressure, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature between 280 ℃, stirring and reacting for 15h, cooling to room temperature after the reaction is finished, discharging, precipitating in acetone, washing the precipitated product with diethyl ether for 4 times, and then removing the diethyl ether by rotary evaporation to obtain benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester;
step S2: 10g of chloromethylsilatrane and 100g of poly (benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester prepared in the step S1 are added into 300g of N-methylpyrrolidone, stirred and reacted for 6 hours at the temperature of 40 ℃, and then the N-methylpyrrolidone is removed by rotary evaporation, the product is washed by diethyl ether for 4 times, and then the diethyl ether is removed by rotary evaporation, so that the chloromethylsilatrane ionized modified poly (benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester is obtained.
The production process of the PBT environment-friendly packaging bag is characterized by comprising the following steps:
step D1: uniformly mixing the raw materials to obtain a mixture, adding the mixture into a double-screw extruder for extrusion, performing tape casting to form a film, and slitting the film by using a slitting machine according to the specification of a packaging bag to obtain a bag piece; the extrusion process parameters are as follows: the temperature of each section of the double-screw extruder is 185 ℃, 195 ℃, 205 ℃, 215 ℃, 225 ℃ and 230 ℃ from the charging opening, and the temperature of the head of the extruder is 220 ℃;
step D2: and (5) die-cutting the bag sheet prepared in the step S1, and then conveying the bag sheet to a bag making machine for making bags to obtain the PBT environment-friendly packaging bag.
Example 2
The PBT environment-friendly packaging bag is characterized by being prepared from the following raw materials in parts by weight: 67 parts of PBT resin, 12 parts of chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 3.5 parts of alginic acid, 5 parts of attapulgite clay powder, 0.35 part of tris (2, 4-di-tert-butylphenyl) phosphite and 0.25 part of polydimethylsiloxane.
The preparation method of the chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester comprises the following steps:
step S1: adding 100g of benzophenone-4, 4' -dicarboxylic acid, 175g of N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, 45g of methylbenzenesulfonic acid and 1150g of N, N-dimethylformamide into a high-pressure reaction kettle, replacing air in the kettle with helium, carrying out esterification reaction for 4.5 hours at the temperature of 237 ℃ and the absolute pressure of 30KPa, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 285 ℃, stirring and reacting for 16h, cooling to room temperature after the reaction is finished, discharging, precipitating in acetone, washing the precipitated product with diethyl ether for 5 times, and then removing the diethyl ether by rotary evaporation to obtain benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester;
step S2: adding 12g of chloromethyl silatrane and 100g of poly benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester prepared in the step S1 into 350g of N-methylpyrrolidone, stirring and reacting for 6.5 hours at 45 ℃, removing the N-methylpyrrolidone by rotary evaporation, washing the product with diethyl ether for 5 times, and removing the diethyl ether by rotary evaporation to obtain the chloromethyl silatrane ionized modified poly benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester.
The production process of the PBT environment-friendly packaging bag is characterized by comprising the following steps:
step D1: uniformly mixing the raw materials to obtain a mixture, adding the mixture into a double-screw extruder for extrusion, performing tape casting to form a film, and slitting the film by using a slitting machine according to the specification of a packaging bag to obtain a bag piece; the extrusion process parameters are as follows: the temperature of each section of the double-screw extruder is 187 ℃, 196 ℃, 206 ℃, 217 ℃, 226 ℃ and 231 ℃ from the charging opening in sequence, and the head temperature of the extruder is 222 DEG C
Step D2: and (5) die-cutting the bag sheet prepared in the step S1, and then conveying the bag sheet to a bag making machine for making bags to obtain the PBT environment-friendly packaging bag.
Example 3
The PBT environment-friendly packaging bag is characterized by being prepared from the following raw materials in parts by weight: 70 parts of PBT resin, 15 parts of chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 4 parts of alginic acid, 6 parts of attapulgite clay powder, 0.4 part of bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and 0.3 part of polydimethylsiloxane.
The preparation method of the chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester comprises the following steps:
step S1: adding 100g of benzophenone-4, 4' -dicarboxylic acid, 175g of N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, 50g of titanium chloride and 1300g of N, N-dimethylacetamide into a high-pressure reaction kettle, replacing air in the kettle with argon, carrying out esterification reaction for 5 hours at the temperature of 240 ℃ and the absolute pressure of 60KPa, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature between 290 ℃, stirring and reacting for 18h, cooling to room temperature after the reaction is finished, discharging, precipitating in acetone, washing the precipitated product with diethyl ether for 6 times, and then removing the diethyl ether by rotary evaporation to obtain benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester;
step S2: adding 15g of chloromethyl silatrane and 100g of poly benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester prepared in the step S1 into 400g of N-methylpyrrolidone, stirring and reacting for 7 hours at 50 ℃, then carrying out rotary evaporation to remove the N-methylpyrrolidone, washing the product with diethyl ether for 6 times, and then carrying out rotary evaporation to remove the diethyl ether to obtain the chloromethyl silatrane ionized modified poly benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester.
The production process of the PBT environment-friendly packaging bag is characterized by comprising the following steps:
step D1: uniformly mixing the raw materials to obtain a mixture, adding the mixture into a double-screw extruder for extrusion, performing tape casting to form a film, and slitting the film by using a slitting machine according to the specification of a packaging bag to obtain a bag piece; the extrusion process parameters are as follows: the temperature of each section of the double-screw extruder is 188 ℃, 197 ℃, 208 ℃, 218 ℃, 227 ℃ and 233 ℃ from a feed inlet in sequence, and the head temperature of the extruder is 225 DEG C
Step D2: and (5) die-cutting the bag sheet prepared in the step S1, and then conveying the bag sheet to a bag making machine for making bags to obtain the PBT environment-friendly packaging bag.
Example 4
The PBT environment-friendly packaging bag is characterized by being prepared from the following raw materials in parts by weight: 73 parts of PBT resin, 18 parts of chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 4.5 parts of alginic acid, 7 parts of attapulgite clay powder, 0.45 part of antioxidant and 0.35 part of lubricant; the lubricant is formed by mixing paraffin and polydimethylsiloxane in a mass ratio of 3: 5; the antioxidant is prepared by mixing tris (2, 4-di-tert-butyl) phenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and dioctadecyl pentaerythritol diphosphite in a mass ratio of 1:1:2: 3.
The preparation method of the chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester comprises the following steps:
step S1: adding 100g of benzophenone-4, 4' -dicarboxylic acid, 175g of N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, 58g of catalyst and 1450g of high-boiling-point solvent into a high-pressure reaction kettle, replacing air in the kettle with neon, carrying out esterification reaction for 5.7 hours at the temperature of 243 ℃ and the absolute pressure of 70KPa, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature to be 297 ℃, stirring for reacting for 19h, cooling to room temperature after the reaction is finished, discharging, precipitating in acetone, washing the precipitated product with diethyl ether for 7 times, and then removing the diethyl ether by rotary evaporation to obtain benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester; the catalyst is formed by mixing tetrabutyl titanate, methyl benzenesulfonic acid and titanium chloride according to the mass ratio of 1:3: 5; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone according to a mass ratio of 1:1:3: 5;
step S2: 19g of chloromethylsilatrane and 100g of poly (benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester prepared in step S1 were added to 480g of N-methylpyrrolidone, and stirred to react at 58 ℃ for 7.8 hours, followed by removal of N-methylpyrrolidone by rotary evaporation, washing of the product with diethyl ether for 7 times, and then removal of diethyl ether by rotary evaporation, to obtain chloromethylsilatrane-ionized modified poly (benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester.
The production process of the PBT environment-friendly packaging bag is characterized by comprising the following steps:
step D1: uniformly mixing the raw materials to obtain a mixture, adding the mixture into a double-screw extruder for extrusion, performing tape casting to form a film, and slitting the film by using a slitting machine according to the specification of a packaging bag to obtain a bag piece; the extrusion process parameters are as follows: the temperature of each section of the double-screw extruder is 189 ℃, 198 ℃, 209 ℃, 218 ℃, 229 ℃ and 234 ℃ from a feed inlet, and the head temperature of the extruder is 228 ℃;
step D2: and (5) die-cutting the bag sheet prepared in the step S1, and then conveying the bag sheet to a bag making machine for making bags to obtain the PBT environment-friendly packaging bag.
Example 5
The PBT environment-friendly packaging bag is characterized by being prepared from the following raw materials in parts by weight: 75 parts of PBT resin, 20 parts of chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 5 parts of alginic acid, 8 parts of attapulgite clay powder, 0.5 part of dioctadecyl pentaerythritol diphosphite and 0.4 part of paraffin.
The preparation method of the chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester comprises the following steps:
step S1: adding 100g of benzophenone-4, 4' -dicarboxylic acid, 175g of N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, 60g of tetrabutyl titanate and 1500g of N-methylpyrrolidone into a high-pressure reaction kettle, replacing the air in the kettle with nitrogen, carrying out esterification reaction for 6 hours at the temperature of 245 ℃ and the absolute pressure of 80KPa, finishing esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature between 300 ℃, stirring and reacting for 20h, cooling to room temperature after the reaction is finished, discharging, precipitating in acetone, washing the precipitated product with diethyl ether for 8 times, and then removing the diethyl ether by rotary evaporation to obtain benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester;
step S2: 20g of chloromethylsilatrane and 100g of poly (benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester prepared in the step S1 are added into 500g of N-methylpyrrolidone, stirred and reacted for 8 hours at the temperature of 60 ℃, and then the N-methylpyrrolidone is removed by rotary evaporation, the product is washed by ethyl ether for 8 times, and then the ethyl ether is removed by rotary evaporation, so that the chloromethylsilatrane ionized modified poly (benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester is obtained.
The production process of the PBT environment-friendly packaging bag is characterized by comprising the following steps:
step D1: uniformly mixing the raw materials to obtain a mixture, adding the mixture into a double-screw extruder for extrusion, performing tape casting to form a film, and slitting the film by using a slitting machine according to the specification of a packaging bag to obtain a bag piece; the extrusion process parameters are as follows: the temperature of each section of the double-screw extruder is from a feed inlet, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ and 235 ℃ in sequence, and the temperature of the extruder head of the extruder is 230 ℃;
step D2: and (5) die-cutting the bag sheet prepared in the step S1, and then conveying the bag sheet to a bag making machine for making bags to obtain the PBT environment-friendly packaging bag.
Comparative example 1
The invention provides a PBT environment-friendly packaging bag, which has a formula and a production process similar to those of example 1, except that chloromethyl aza-silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester is not added.
Comparative example 2
The invention provides a PBT environment-friendly packaging bag, which has a formula and a production process similar to those of example 1, except that alginic acid and attapulgite clay powder are not added.
Comparative example 3
The invention provides a PBT environment-friendly packaging bag, which has a formula and a production process similar to those of example 1, except that poly-benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester is used for replacing chloromethyl aza-silazane trialkyl-ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester.
Comparative example 4
The invention provides a commercially available packaging bag, which mainly comprises PET and is purchased from Shandong company.
The PBT environmental protection packaging bags produced by the above examples 1-5 and comparative examples 1-3 were subjected to the relevant performance tests, and the test results and the test methods are shown in Table 1.
TABLE 1
| Item | Tensile strength | Amount of wear | Notched impact strength 23 deg.C |
| Unit of | MPa | mg | KJ/m2 |
| Test standard | GB/T1040 | GB/T25262-2010 | GB/T20186.1-2006 |
| Example 1 | 84 | 2.5 | 8.5 |
| Example 2 | 88 | 2.3 | 8.7 |
| Example 3 | 93 | 2.2 | 8.8 |
| Example 4 | 95 | 2.0 | 9.1 |
| Example 5 | 98 | 1.8 | 9.4 |
| Comparative example 1 | 68 | 3.5 | 7.2 |
| Comparative example 2 | 70 | 3.6 | 7.5 |
| Comparative example 3 | 65 | 3.3 | 6.7 |
| Comparative example 4 | 58 | 3.8 | 6.4 |
As can be seen from Table 1, the PBT environment-friendly packaging bag disclosed by the embodiment of the invention has excellent mechanical properties and wear resistance, which are the result of synergistic effect of the raw materials.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The PBT environment-friendly packaging bag is characterized by being prepared from the following raw materials in parts by weight: 65-75 parts of PBT resin, 10-20 parts of chloromethyl aza-silazane-ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester, 3-5 parts of alginic acid, 4-8 parts of attapulgite clay powder, 0.3-0.5 part of antioxidant and 0.2-0.4 part of lubricant.
2. The environment-friendly PBT packaging bag according to claim 1, wherein the lubricant is at least one of paraffin wax and polydimethylsiloxane.
3. The environment-friendly PBT packaging bag according to claim 1, wherein the antioxidant is at least one selected from the group consisting of tris (2, 4-di-tert-butyl) phenyl phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite and dioctadecyl pentaerythritol diphosphite.
4. The PBT environment-friendly packaging bag as claimed in claim 1, wherein the preparation method of chloromethyl aza silazane trialkyl ionized modified poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester comprises the following steps:
step S1: adding benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, a catalyst and a high-boiling point solvent into a high-pressure reaction kettle, replacing air in the kettle with nitrogen or inert gas, then carrying out esterification reaction for 4-6 hours under the conditions of the temperature of 235-245 ℃ and the absolute pressure of 20-80 KPa, ending esterification, and relieving pressure to normal pressure; then under the vacuum condition, controlling the temperature between 280 ℃ and 300 ℃, stirring and reacting for 15-20h, cooling to room temperature after the reaction is finished, discharging and precipitating in acetone, washing the precipitated product with diethyl ether for 4-8 times, and then removing the diethyl ether by rotary evaporation to obtain benzophenone-4, 4' -dicarboxylic acid, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester;
step S2: chloromethyl aza silatrane and poly benzophenone-4, 4 '-dicarboxylic acid N, N' -bis (2-hydroxyethyl) -N, N '-bis (trimethoxysilylpropyl) ethylenediamine ester prepared in the step S1 are added into N-methyl pyrrolidone to be stirred and reacted for 6 to 8 hours at the temperature of 40 to 60 ℃, then the N-methyl pyrrolidone is removed by rotary evaporation, the product is washed by ethyl ether for 4 to 8 times, and then the ethyl ether is removed by rotary evaporation, thus obtaining the chloromethyl aza silatrane ionized modified poly benzophenone-4, 4' -dicarboxylic acid N, N '-bis (2-hydroxyethyl) -N, N' -bis (trimethoxysilylpropyl) ethylenediamine ester.
5. The PBT environment-friendly packaging bag according to claim 4, wherein the mass ratio of the benzophenone-4, 4' -dicarboxylic acid, the N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine, the catalyst and the high boiling point solvent in the step S1 is 1:1.75 (0.4-0.6): 10-15.
6. The environment-friendly PBT packaging bag according to claim 4, wherein the catalyst is at least one of tetrabutyl titanate, methyl benzene sulfonic acid and titanium chloride; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone; the inert gas is one of helium, neon and argon.
7. The PBT environment-friendly packaging bag according to claim 4, wherein the mass ratio of the chloromethyl aza-silazane to the poly-benzophenone-4, 4' -dicarboxylic acid N, N ' -bis (2-hydroxyethyl) -N, N ' -bis (trimethoxysilylpropyl) ethylenediamine ester to the N-methylpyrrolidone in step S2 is (0.1-0.2):1 (3-5).
8. The environment-friendly PBT packaging bag according to any one of claims 1 to 7, wherein the production process of the environment-friendly PBT packaging bag comprises the following steps:
step D1: uniformly mixing the raw materials to obtain a mixture, adding the mixture into a double-screw extruder for extrusion, performing tape casting to form a film, and slitting the film by using a slitting machine according to the specification of a packaging bag to obtain a bag piece;
step D2: and (5) die-cutting the bag sheet prepared in the step S1, and then conveying the bag sheet to a bag making machine for making bags to obtain the PBT environment-friendly packaging bag.
9. The PBT environmental protection packaging bag of claim 8, wherein the extrusion process parameters in D1 are: the temperature of each section of the double-screw extruder is from a charging opening to 185-plus-190 ℃, 195-plus-200 ℃, 205-plus-210 ℃, 215-plus-220 ℃, 225-plus-230 ℃ and 230-plus-235 ℃ in sequence, and the temperature of the head of the extruder is 220-plus-230 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911210978.XA CN111057351B (en) | 2019-12-02 | 2019-12-02 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911210978.XA CN111057351B (en) | 2019-12-02 | 2019-12-02 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111057351A true CN111057351A (en) | 2020-04-24 |
| CN111057351B CN111057351B (en) | 2022-03-18 |
Family
ID=70299322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911210978.XA Active CN111057351B (en) | 2019-12-02 | 2019-12-02 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111057351B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534059A (en) * | 2020-05-19 | 2020-08-14 | 苏州市新广益电子有限公司 | High-temperature-resistant PBT (polybutylene terephthalate) aroma-preserving lunch box capable of being used in microwave oven |
| CN112375293A (en) * | 2020-11-12 | 2021-02-19 | 韩先锋 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
| CN113788219A (en) * | 2021-08-20 | 2021-12-14 | 张敏 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
| CN114957934A (en) * | 2022-06-27 | 2022-08-30 | 扬州君禾薄膜科技有限公司 | Antibacterial antistatic polyester chip and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944442A (en) * | 2006-10-30 | 2007-04-11 | 温州医学院 | Preparation of 3,7,10-tri-substuent hetero nitrogen silicon tricyclic and 5-Fu combined substance and its use in pharmacy |
| CN105331056A (en) * | 2015-11-12 | 2016-02-17 | 界首市东威塑业有限公司 | Modified plastic granules for processing automobile door outer handle |
| CN106496848A (en) * | 2016-11-01 | 2017-03-15 | 金福兴 | A kind of composite resin medical infusion bags material and preparation method thereof |
| CN109438906A (en) * | 2018-10-18 | 2019-03-08 | 吴江市英力达塑料包装有限公司 | A kind of preparation method of elastic shock attenuation plastic package material |
| KR20190062709A (en) * | 2017-11-29 | 2019-06-07 | 주식회사 울트라브이 | The fabrication method of fine particle of biodegradable polymer, the fabrication method of injection including the same, and reactor for manufacturing fine particle of biodegradable polymer |
| CN110437572A (en) * | 2019-07-22 | 2019-11-12 | 邓华斌 | A kind of glass fiber reinforced plastics composite material and preparation method thereof |
-
2019
- 2019-12-02 CN CN201911210978.XA patent/CN111057351B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944442A (en) * | 2006-10-30 | 2007-04-11 | 温州医学院 | Preparation of 3,7,10-tri-substuent hetero nitrogen silicon tricyclic and 5-Fu combined substance and its use in pharmacy |
| CN105331056A (en) * | 2015-11-12 | 2016-02-17 | 界首市东威塑业有限公司 | Modified plastic granules for processing automobile door outer handle |
| CN106496848A (en) * | 2016-11-01 | 2017-03-15 | 金福兴 | A kind of composite resin medical infusion bags material and preparation method thereof |
| KR20190062709A (en) * | 2017-11-29 | 2019-06-07 | 주식회사 울트라브이 | The fabrication method of fine particle of biodegradable polymer, the fabrication method of injection including the same, and reactor for manufacturing fine particle of biodegradable polymer |
| CN109438906A (en) * | 2018-10-18 | 2019-03-08 | 吴江市英力达塑料包装有限公司 | A kind of preparation method of elastic shock attenuation plastic package material |
| CN110437572A (en) * | 2019-07-22 | 2019-11-12 | 邓华斌 | A kind of glass fiber reinforced plastics composite material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534059A (en) * | 2020-05-19 | 2020-08-14 | 苏州市新广益电子有限公司 | High-temperature-resistant PBT (polybutylene terephthalate) aroma-preserving lunch box capable of being used in microwave oven |
| CN111534059B (en) * | 2020-05-19 | 2023-01-13 | 苏州市新广益电子股份有限公司 | High temperature resistant PBT (polybutylene terephthalate) aroma-preserving lunch box capable of being used in microwave oven |
| CN112375293A (en) * | 2020-11-12 | 2021-02-19 | 韩先锋 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
| CN113788219A (en) * | 2021-08-20 | 2021-12-14 | 张敏 | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof |
| CN114957934A (en) * | 2022-06-27 | 2022-08-30 | 扬州君禾薄膜科技有限公司 | Antibacterial antistatic polyester chip and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111057351B (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111057351B (en) | PBT (polybutylene terephthalate) environment-friendly packaging bag and production process thereof | |
| CN1048026C (en) | Composite sheet | |
| KR102050710B1 (en) | Multi-layered structure and manufacturing method thereof, packaging materials and products using same, and protective sheet of electronic device | |
| CN108026337B (en) | Rubber composition | |
| CN110760169A (en) | Barrier material and preparation method thereof | |
| CN115466565B (en) | Coating composition for packaging photovoltaic module, preparation method of composite material for packaging and photovoltaic module | |
| CN113087973A (en) | Biodegradable high-temperature-resistant disposable tableware and preparation method thereof | |
| KR101983541B1 (en) | Antistatic sheet, and packaging material and electronic device including same | |
| CN117343504B (en) | Ultraviolet aging resistant polyester material and preparation method thereof | |
| CN110395027A (en) | A kind of highlighted polyester film and its manufacturing method | |
| CN111730943B (en) | Degradable biological plastic composite paper and preparation process thereof | |
| JP6500089B2 (en) | Antistatic sheet and packaging material and electronic device including the same | |
| CN111849011A (en) | Preparation method of high-barrier recyclable plastic and composite hose | |
| KR102210477B1 (en) | Multilayer plastic card | |
| WO2016031626A1 (en) | Polyolefin resin composition, molding, and polyolefin resin film | |
| CN113583438B (en) | Biodegradable alkali lignin composite material, preparation method and application thereof | |
| WO2007027043A1 (en) | Copolyester resin composition for profile extrusion molding and molded articles made from the same | |
| CN112920568A (en) | Biodegradable express packaging bag and preparation method thereof | |
| CN110746753B (en) | PET film blowing bag and preparation method thereof | |
| CN111454470A (en) | Modified aramid fiber and rubber composite material and preparation method thereof | |
| Thomas et al. | Engineering and Specialty Thermoplastics: Polyethers and Polyesters: State‐of‐the‐art, New Challenges and Opportunities | |
| KR20200005340A (en) | Aliphatic polycarbonate copolymer resin and packaging film using same | |
| KR102399123B1 (en) | Eco-friendly air cap and manufacturing method of thereof | |
| CN116693940B (en) | Coated flame retardant, structural member, battery pack, power utilization device and preparation method | |
| CN117186597A (en) | Environment-friendly type barrier film packaging material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 215156 Building 1, 289 Caofeng Road, Xukou Town, Wuzhong District, Suzhou City, Jiangsu Province Patentee after: Suzhou New Guangyi Electronics Co.,Ltd. Address before: 215156 Building 1, 289 Caofeng Road, Xukou Town, Wuzhong District, Suzhou City, Jiangsu Province Patentee before: SUZHOU XINGUANGYI ELECTRONICS Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |