CN107163223A - A kind of photochromic TPU film of high temperature resistant and preparation method thereof - Google Patents
A kind of photochromic TPU film of high temperature resistant and preparation method thereof Download PDFInfo
- Publication number
- CN107163223A CN107163223A CN201710520799.0A CN201710520799A CN107163223A CN 107163223 A CN107163223 A CN 107163223A CN 201710520799 A CN201710520799 A CN 201710520799A CN 107163223 A CN107163223 A CN 107163223A
- Authority
- CN
- China
- Prior art keywords
- high temperature
- temperature resistant
- tpu film
- photochromic
- preparation
- 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.)
- Withdrawn
Links
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
- C08G18/70—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The present invention relates to a kind of photochromic TPU film of high temperature resistant, it is characterized in that, the raw material of the photochromic TPU film of high temperature resistant includes 4,4 ' methyl diphenylene diisocyanates, PPG, chain extender, azodiisobutyronitrile and catalyst, the mass ratio of wherein described 4,4 ' methyl diphenylene diisocyanate and azodiisobutyronitrile is (5~15):1.The photochromic TPU film luminous sensitivity of high temperature resistant is high, and nondiscolouring at high temperature, and physical property is good, simple production process, available for industrialized production.
Description
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of photochromic TPU film of high temperature resistant and its preparation side
Method.
Background technology
Thermoplastic polyurethane (TPU) is a kind of new organic polymer synthetic material, and its properties is excellent, Ke Yidai
For rubber, soft polyvinyl chloride material PVC.TPU has excellent physical property, such as wearability, and screen resilience is all better than common
Polyurethane and PVC, resistance to ag(e)ing are better than rubber, it may be said that be the optimal material for substituting PVC and PU.
Photochromic article, the particularly photochromic plastic materials for optical application, it has also become the master received much attention
Topic.Particularly, photochromic ophthalmically acceptable lucite eyeglass is shown compared to simple glass eyeglass by it weight advantage and resistance to
Impact, has obtained commercial interest.In addition, photochromic transparent lamella, for example, on the vehicles such as automobile, ship and aircraft
Photochromic glass window, because the potential security feature that the transparent sheet is shown has caused the interest of people.
The A of CN 105254910 disclose a kind of photochromic film material and preparation method thereof, the photochromic film
Material, is by mass percentage 20-50% by tertiary amine-type benzoic ether, salicylate is 1-15%, and BTA is 1-
5%, organic siliconresin is 5-50%, and curing agent is 0.5-5%, and phosphomolybdic acid constitutes for 10-25%;Wherein described organic siliconresin
Mass ratio with curing agent is 10:1;The preparation method, will be matched, load weighted tertiary amine-type benzoic acid by mass percentage
Ester, salicylate, BTA, organic siliconresin and phosphomolybdic acid, are placed on mixed with 300r/min speed stirring in mixer
0.5-1.0h is closed, curing agent is then added, continues to stir 0.5h with 300r/min rotating speed, silk screen or spray is used after being well mixed
The method of ink print is coated on polyurethane film, and photochromic film material is obtained after being dried under the conditions of 25-150 DEG C.Should
Invention combines phosphomolybdic acid with BTA, improves photochromic sensitivity, but the photochromic film material is only
It is that light-sensitive compound by necessarily matching is coated in polyurethane surface, for a long time using occurring that coat comes off, while double
The refractive index difference of tunic can cause light different from theoretical value through color after film, therefore the manufacture difficulty of the thin-film material
Greatly, and service life is short.
The A of CN 1824686 disclose photochromic polyurethane of a kind of high temperature resistant and preparation method thereof, and the high temperature resistant is photic
Color-changing polyurethane with 4,4 '-bis- [(4- amino) thiophenyl] benzophenone are diamine monomer, the spirit designed using polyurethane molecular
The isocyanates of activity, the diamine monomer and bifunctionality, the dihydric alcohol containing tertiary amine structure react by Step Condensation, and end is made
The light sensitive polyurethane of hydroxyl or Amino End Group.Contain benzophenone and hydrogen donor tertiary amine structure in the compound simultaneously, it can
To be used separately as a kind of novel high polymer light trigger, the polyurethane prepolymer that can act also as low molecule amount is used or is used for
Prepare other photosensitive materials.The photochromic polyurethane material of high temperature resistant described in the invention is to pass through sulfide linkage under ultraviolet light
It is broken to produce free radical, and then reaches the effect of photocuring.Although photosensitive group is introduced into the main chain of polyurethane by the present invention,
Be conducive to the preparation of polyurethane film, but be incorporated into main chain and controlled by changing the ratio of the degree of polymerization and polymerized monomer
The difficulty of photosensitive degree is big, due to the poor controllability of the degree of polymerization, causes the polyurethane uncontrollability high, it is difficult to be applied.
Meanwhile, photochromic TPU film in the prior art, at room temperature changeable colour, but color is unstable in high temperature environments
Fixed, color produces uncontrollable change.
Therefore, in order to solve the above problems, a kind of research photochromic TPU film of more preferable high temperature resistant of performance is very heavy
Will.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of photochromic TPU film of high temperature resistant and preparation method thereof, institute
State the photochromic TPU film luminous sensitivity of high temperature resistant high, and nondiscolouring at high temperature, well, production technology is simple for physical property
It is single, available for industrialized production.
For up to this purpose, the present invention uses following technical scheme:
One of the object of the invention is to provide a kind of high temperature resistant photochromic TPU film, it is characterised in that the high temperature resistant
It is different that the raw material of photochromic TPU film includes 4,4 '-methyl diphenylene diisocyanate, PPG, chain extender, azo two
Butyronitrile and catalyst, wherein described 4, the mass ratio of 4 '-methyl diphenylene diisocyanate and azodiisobutyronitrile for (5~
15):1。
The mass ratio of the 4,4 '-methyl diphenylene diisocyanate and azodiisobutyronitrile can be 5:1、6:1、7:1、
8:1、9:1、10:1、11:1、12:1、13:1、14:1 or 15:1 etc., it is not limited to cited numerical value, the number range
Other interior unrequited numerical value are equally applicable.
There is azo bond in the molecular structure of azodiisobutyronitrile, and photoisomerization can occur under light illumination for azo bond,
So as to cause the phenyl ring conjugated system in azodiisobutyronitrile to change, and then cause the light absorbing wavelength of azodiisobutyronitrile
Change, so as to cause film to change colour, but azodiisobutyronitrile can become the structure before illumination again at high temperature, and 4,4 '-
There are two phenyl ring in methyl diphenylene diisocyanate, can effectively stablize azodiisobutyronitrile it is photochromic after molecule knot
Structure, makes it still keep the configuration after illumination at high temperature.Another aspect azodiisobutyronitrile is easily decomposed at high temperature, 4,4 '-
Methyl diphenylene diisocyanate can stablize azodiisobutyronitrile, it is not decomposed at high temperature, it is ensured that its processing characteristics.
Below as currently preferred technical scheme, but the limitation of the technical scheme provided not as the present invention, pass through
Following technical scheme, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, the photochromic TPU film of high temperature resistant it is main by weight by with
Lower raw material is prepared:
The mass parts of wherein described 4,4 '-methyl diphenylene diisocyanate can be 30 parts, 32 parts, 35 parts, 38 parts, 40
Part, 42 parts or 45 parts etc.;The mass parts of the PPG can be 70 parts, 72 parts, 76 parts, 78 parts, 80 parts, 82 parts, 86
Part, 88 parts or 90 parts etc.;The mass parts of the chain extender can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts etc.;It is described
The mass parts of azodiisobutyronitrile can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts or 6 parts etc.;The matter of the catalyst
It can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts etc. to measure part;It is not limited to cited numerical value, in above-mentioned each number range its
His unrequited numerical value is equally applicable.
As currently preferred technical scheme, the photochromic TPU film of high temperature resistant it is main by weight by with
Lower raw material is prepared:
As currently preferred technical scheme, the photochromic TPU film of high temperature resistant it is main by weight by with
Lower raw material is prepared:
As currently preferred technical scheme, aromatics group is free of on the main chain and side chain of the PPG.
Preferably, the number-average molecular weight of the PPG be 3000~4000, such as 3000,3100,3200,3300,
3400th, 3500,3600,3700,3800,3900 or 4000 etc., it is not limited to cited numerical value, in the number range its
His unrequited numerical value is equally applicable.
As currently preferred technical scheme, the chain extender be selected from ethylene glycol, 1,3-PD, BDO or
In 1,5-PD any one or at least two combination, combination typical case but non-limiting examples have:Ethylene glycol and
The combination of 1,3- propane diols, the combination of 1,3- propane diols and 1,4- butanediols, combination, the second of 1,4- butanediols and 1,5- pentanediols
The combination of glycol and 1,5- pentanediols or the combination of ethylene glycol, 1,3- propane diols and 1,4- butanediols etc..
Preferably, the catalyst is any one in stannous octoate, two sad two fourths tin or dibutyl tin dilaurate
Or at least two combination, combination typical case but non-limiting examples have:The combination of stannous octoate and two sad two fourths tin, two
The combinations of sad two fourth tin and dibutyl tin dilaurate, the combination of dibutyl tin dilaurate and stannous octoate or stannous octoate, two
Combination of sad two fourth tin and dibutyl tin dilaurate etc..
The two of the object of the invention are to provide a kind of preparation method of the described photochromic TPU film of high temperature resistant, described
Preparation method comprises the following steps:
(1) by the PPG of formula ratio and 4,4 '-methyl diphenylene diisocyanate is sequentially added in container, is being stirred
Vacuumized under the conditions of mixing in 50~60 DEG C, obtain performed polymer;
(2) chain extender and catalyst of formula ratio are added in the performed polymer obtained to step (1), continues anti-in 70~80 DEG C
Answer 2~4h;
(3) azodiisobutyronitrile of formula ratio is added in reacted material into step (2), 1~2h, Ran Houjia is stirred
Enter extrusion molding in double screw extruder and obtain the photochromic TPU film of high temperature resistant.
Wherein, step (1) temperature that vacuumizes can be 50 DEG C, 51 DEG C, 52 DEG C, 53 DEG C, 54 DEG C, 55 DEG C, 56 DEG C,
57 DEG C, 58 DEG C, 59 DEG C or 60 DEG C etc.;Step (2) described reaction temperature can be 70 DEG C, 71 DEG C, 72 DEG C, 73 DEG C, 74 DEG C, 75
DEG C, 76 DEG C, 77 DEG C, 78 DEG C, 79 DEG C or 80 DEG C etc.;The time of step (2) described reaction can be 2h, 2.2h, 2.5h, 2.8h,
3h, 3.2h, 3.5h, 3.8h or 4h etc.;The time of step (3) described stirring can be 1h, 1.1h, 1.2h, 1.3h, 1.4h,
1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h etc.;It is not limited to cited numerical value, in above-mentioned each number range other
Unrequited numerical value is equally applicable.
As currently preferred technical scheme, the stir speed (S.S.) described in step (1) is 500~1000r/min, such as
500r/min, 600r/min, 700r/min, 800r/min, 900r/min or 1000r/min etc., it is not limited to cited
Numerical value, other unrequited numerical value are equally applicable in the number range.
Preferably, the vacuum of the vacuum described in step (1) be -0.4~-0.2kPa, such as -0.4kPa, -0.38kPa, -
0.35kPa, -0.32kPa, -0.30kPa, -0.28kPa, -0.25kPa, -0.22kPa or -0.20kPa etc., it is not limited to
Other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, the stir speed (S.S.) described in step (3) is 500~1000r/min such as 500r/
Min, 600r/min, 700r/min, 800r/min, 900r/min or 1000r/min etc., it is not limited to cited number
Other unrequited numerical value are equally applicable in value, the number range.
As currently preferred technical scheme, the feeding section temperature that double screw extruder is set in the step (3) is
130~140 DEG C, such as 130 DEG C, 131 DEG C, 132 DEG C, 133 DEG C, 134 DEG C, 135 DEG C, 136 DEG C, 137 DEG C, 138 DEG C, 139 DEG C or 140
DEG C etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, the mixing section temperature that double screw extruder is set in step (3) is 150~160 DEG C, such as 150 DEG C, 151
DEG C, 152 DEG C, 153 DEG C, 154 DEG C, 155 DEG C, 156 DEG C, 157 DEG C, 158 DEG C, 159 DEG C or 160 DEG C etc., it is not limited to listed
Other unrequited numerical value are equally applicable in the numerical value of act, the number range.
Preferably, the extruding zone temperature that double screw extruder is set in step (3) is 170~180 DEG C, such as 170 DEG C, 171
DEG C, 172 DEG C, 173 DEG C, 174 DEG C, 175 DEG C, 176 DEG C, 177 DEG C, 178 DEG C, 179 DEG C or 180 DEG C etc., it is not limited to listed
Other unrequited numerical value are equally applicable in the numerical value of act, the number range.
Preferably, the head temperature that double screw extruder is set in step (3) is 170~180 DEG C, such as 170 DEG C, 171 DEG C,
172 DEG C, 173 DEG C, 174 DEG C, 175 DEG C, 176 DEG C, 177 DEG C, 178 DEG C, 179 DEG C or 180 DEG C etc., it is not limited to cited
Other unrequited numerical value are equally applicable in numerical value, the number range.
Relative to prior art, the invention has the advantages that:
(1) the photochromic TPU film of a kind of high temperature resistant that the present invention is provided, using azodiisobutyronitrile as emulsion,
4,4 '-methyl diphenylene diisocyanate acts synergistically with azodiisobutyronitrile, after the TPU film can be made photochromic again
Nondiscolouring under high temperature, enhances the light sensitivity of TPU film.
(2) a kind of photochromic TPU film of high temperature resistant that the present invention is provided, tensile strength reaches 75MPa, and elongation at break reaches
452%, rebound degree is up to 95%, with good physical property.
(3) a kind of preparation method technique for the photochromic TPU film of high temperature resistant that the present invention is provided is simple, available for industry
Metaplasia is produced.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
A kind of preparation method of the photochromic TPU film of high temperature resistant, the described method comprises the following steps:
(1) by 70 parts of PPGs (number-average molecular weight 3500) and 30 parts of 4,4 '-methyl diphenylene diisocyanates according to
In secondary addition container, stirred under 500r/min speed, be evacuated to -0.4kPa in 50 DEG C, obtain performed polymer;
(2) the 10 parts of chain extenders and 1 part of catalyst of formula ratio are added in the performed polymer obtained to step (1), in 70 DEG C after
Continuous reaction 2h;
(3) 6 parts of azodiisobutyronitriles are added in reacted material into step (2), are stirred under 500r/min speed
1h is mixed, is then added in double screw extruder, the feeding section temperature for setting double screw extruder is 130 DEG C, mixing section temperature
For 150 DEG C, extruding zone temperature is 170 DEG C, and head section temperature is 170 DEG C, and extrusion molding obtains the photochromic TPU film of high temperature resistant.
Embodiment 2
A kind of preparation method of the photochromic TPU film of high temperature resistant, the described method comprises the following steps:
(1) by 86 parts of PPGs (number-average molecular weight 3200) and 42 parts of 4,4 '-methyl diphenylene diisocyanates according to
In secondary addition container, stirred under 1000r/min speed, be evacuated to -0.35kPa in 58 DEG C, obtain performed polymer;
(2) the 14 parts of chain extenders and 2 parts of catalyst of formula ratio are added in the performed polymer obtained to step (1), in 78 DEG C after
Continuous reaction 3.5h;
(3) 5.5 parts of azodiisobutyronitriles are added in reacted material into step (2), under 1000r/min speed
1.8h is stirred, is then added in double screw extruder, the feeding section temperature for setting double screw extruder is 138 DEG C, mixing section
Temperature is 158 DEG C, and extruding zone temperature is 178 DEG C, and head section temperature is 178 DEG C, and extrusion molding obtains the photochromic TPU of high temperature resistant
Film.
Embodiment 3
A kind of preparation method of the photochromic TPU film of high temperature resistant, the described method comprises the following steps:
(1) by 82 parts of PPGs (number-average molecular weight 3800) and 38 parts of 4,4 '-methyl diphenylene diisocyanates according to
In secondary addition container, stirred under 900r/min speed, be evacuated to -0.3kPa in 55 DEG C, obtain performed polymer;
(2) the 13 parts of chain extenders and 3 parts of catalyst of formula ratio are added in the performed polymer obtained to step (1), in 75 DEG C after
Continuous reaction 3h;
(3) 5 parts of azodiisobutyronitriles are added in reacted material into step (2), are stirred under 900r/min speed
1.5h is mixed, is then added in double screw extruder, the feeding section temperature for setting double screw extruder is 135 DEG C, mixing section temperature
For 155 DEG C, extruding zone temperature is 175 DEG C, and head section temperature is 175 DEG C, and extrusion molding obtains the photochromic TPU film of high temperature resistant.
Embodiment 4
A kind of preparation method of the photochromic TPU film of high temperature resistant, the described method comprises the following steps:
(1) by 76 parts of PPGs (number-average molecular weight 3000) and 35 parts of 4,4 '-methyl diphenylene diisocyanates according to
In secondary addition container, stirred under 800r/min speed, be evacuated to -0.25kPa in 52 DEG C, obtain performed polymer;
(2) the 12 parts of chain extenders and 2 parts of catalyst of formula ratio are added in the performed polymer obtained to step (1), in 72 DEG C after
Continuous reaction 2.5h;
(3) 4 parts of azodiisobutyronitriles are added in reacted material into step (2), are stirred under 800r/min speed
1.2h is mixed, is then added in double screw extruder, the feeding section temperature for setting double screw extruder is 132 DEG C, mixing section temperature
For 152 DEG C, extruding zone temperature is 172 DEG C, and head section temperature is 172 DEG C, and extrusion molding obtains the photochromic TPU film of high temperature resistant.
Embodiment 5
A kind of preparation method of the photochromic TPU film of high temperature resistant, the described method comprises the following steps:
(1) by 90 parts of PPGs (number-average molecular weight 4000) and 45 parts of 4,4 '-methyl diphenylene diisocyanates according to
In secondary addition container, stirred under 1000r/min speed, be evacuated to -0.2kPa in 60 DEG C, obtain performed polymer;
(2) the 15 parts of chain extenders and 5 parts of catalyst of formula ratio are added in the performed polymer obtained to step (1), in 80 DEG C after
Continuous reaction 4h;
(3) 3 parts of azodiisobutyronitriles are added in reacted material into step (2), are stirred under 1000r/min speed
2h is mixed, is then added in double screw extruder, the feeding section temperature for setting double screw extruder is 140 DEG C, mixing section temperature
For 160 DEG C, extruding zone temperature is 180 DEG C, and head section temperature is 180 DEG C, and extrusion molding obtains the photochromic TPU film of high temperature resistant.
Comparative example 1
A kind of preparation method of the photochromic TPU film of high temperature resistant, in addition to adding 38 parts of azodiisobutyronitriles (i.e. 4,
The mass ratio of 4 '-methyl diphenylene diisocyanate and azodiisobutyronitrile is 1:1), other conditions are same as Example 3.
Comparative example 2
A kind of preparation method of the photochromic TPU film of high temperature resistant, in addition to adding 1.9 parts of azodiisobutyronitriles (i.e. 4,
The mass ratio of 4 '-methyl diphenylene diisocyanate and azodiisobutyronitrile is 20:1), other conditions are same as Example 3.
Comparative example 3
A kind of preparation method of the photochromic TPU film of high temperature resistant, in addition to being added without azodiisobutyronitrile, other conditions
It is same as Example 3.
Comparative example 4
A kind of preparation method of the photochromic TPU film of high temperature resistant, except with IPDI replace 4,4 '-
Outside methyl diphenylene diisocyanate, other conditions are same as Example 3.
Comparative example 5
A kind of preparation method of the photochromic TPU film of high temperature resistant, except with IPDI replace 4,4 '-
Methyl diphenylene diisocyanate, and without 5 parts of azodiisobutyronitriles outside, other conditions are same as Example 3.
The photochromic TPU film of high temperature resistant prepared to embodiment 1-5 and comparative example 1-5 is under visible light illumination
Photochromic test is carried out, and the film after discoloration is handled into 2h at 250 DEG C observing its color change and physical property survey
Examination, test result is shown in Table 1.
Table 1
As it can be seen from table 1 the TPU film that embodiment 1-5 is prepared can be changed into red from colourless under visible light illumination
Color, and the film after changing colour handles 2h at 250 DEG C, film can still keep original red nondiscolouring, and prepared by embodiment 1-5
The tensile strength of obtained TPU film reaches 75MPa, and elongation at break is up to 452%, and rebound degree is up to 95%, with good physics
Performance.And the mass ratio of 4,4 '-methyl diphenylene diisocyanate and azodiisobutyronitrile is distinguished in comparative example 1 and comparative example 2
Below or above (5~15):1 scope, so that comparative example 1 is changed into shallower Huang in high-temperature process rear film from red
Color, and the nondiscolouring under visible light illumination of comparative example 2.Comparative example 3-5 is due to without azodiisobutyronitrile or using isophorone
Diisocyanate replaces 4, and 4 '-methyl diphenylene diisocyanate causes TPU film not have the colour change function of light.
Applicant states that the present invention illustrates the detailed preparation flow of the present invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed preparation flow is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed preparation flow and could implemented.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of each raw material of product of the present invention
And addition, the selection of concrete mode of auxiliary element etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of photochromic TPU film of high temperature resistant, it is characterised in that the raw material bag of the photochromic TPU film of high temperature resistant
Include 4,4 '-methyl diphenylene diisocyanate, PPG, chain extender, azodiisobutyronitrile and catalyst, wherein described
The mass ratio of 4,4 '-methyl diphenylene diisocyanate and azodiisobutyronitrile is (5~15):1.
2. the photochromic TPU film of high temperature resistant according to claim 1, it is characterised in that the high temperature resistant is photochromic
The raw material of TPU film includes following component by weight:
3. the photochromic TPU film of high temperature resistant according to claim 1 or 2, it is characterised in that the high temperature resistant light-induced variable
The raw material of color TPU film includes following component by weight:
4. the photochromic TPU film of high temperature resistant according to claim any one of 1-3, it is characterised in that the high temperature resistant
The raw material of photochromic TPU film includes following component by weight:
5. the photochromic TPU film of high temperature resistant according to claim any one of 1-4, it is characterised in that the polyethers is more
Aromatics group is free of on the main chain and side chain of first alcohol;
Preferably, the number-average molecular weight of the PPG is 3000~4000.
6. the photochromic TPU film of high temperature resistant according to claim any one of 1-5, it is characterised in that the chain extender
In ethylene glycol, 1,3- propane diols, 1,4- butanediols or 1,5- pentanediols any one or at least two combination;
Preferably, the catalyst be stannous octoate, two sad two fourths tin or dibutyl tin dilaurate in any one or extremely
Few two kinds combination.
7. the preparation method of the photochromic TPU film of high temperature resistant according to claim any one of 1-6, it is characterised in that
The preparation method comprises the following steps:
(1) by the PPG of formula ratio and 4,4 '-methyl diphenylene diisocyanate is sequentially added in container, in stirring bar
Vacuumized under part in 50~60 DEG C, obtain performed polymer;
(2) chain extender and catalyst of formula ratio are added in the performed polymer obtained to step (1), continues to react 2 in 70~80 DEG C
~4h;
(3) azodiisobutyronitrile of formula ratio is added in reacted material into step (2), 1~2h is stirred, then added double
Extrusion molding obtains the photochromic TPU film of high temperature resistant in screw extruder.
8. preparation method according to claim 7, it is characterised in that stir speed (S.S.) described in step (1) for 500~
1000r/min;
Preferably, the vacuum of the vacuum described in step (1) is -0.4~-0.2kPa.
9. the preparation method according to claim 7 or 8, it is characterised in that stir speed (S.S.) described in step (3) for 500~
1000r/min。
10. the preparation method according to claim any one of 7-9, it is characterised in that twin-screw is set in the step (3)
The feeding section temperature of extruder is 130~140 DEG C;
Preferably, the mixing section temperature that double screw extruder is set in step (3) is 150~160 DEG C;
Preferably, the extruding zone temperature that double screw extruder is set in step (3) is 170~180 DEG C;
Preferably, the head temperature that double screw extruder is set in step (3) is 170~180 DEG C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710520799.0A CN107163223A (en) | 2017-06-30 | 2017-06-30 | A kind of photochromic TPU film of high temperature resistant and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710520799.0A CN107163223A (en) | 2017-06-30 | 2017-06-30 | A kind of photochromic TPU film of high temperature resistant and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107163223A true CN107163223A (en) | 2017-09-15 |
Family
ID=59827343
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710520799.0A Withdrawn CN107163223A (en) | 2017-06-30 | 2017-06-30 | A kind of photochromic TPU film of high temperature resistant and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107163223A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109517120A (en) * | 2018-11-12 | 2019-03-26 | 安徽富瑞雪化工科技股份有限公司 | A kind of urethane acrylate discoloration lotion and preparation method |
CN111019166A (en) * | 2019-12-03 | 2020-04-17 | 东莞市雄林新材料科技股份有限公司 | TPU film with adjustable color opening and preparation method thereof |
CN111040422A (en) * | 2019-12-03 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Skin-feel TPU film and preparation method thereof |
CN111040425A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Polarity-adjustable TPU film and preparation method thereof |
CN111040423A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Electroluminescence color-changing TPU film and preparation method thereof |
CN111040424A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Transparency-controllable TPU (thermoplastic polyurethane) film and preparation method thereof |
CN112048053A (en) * | 2020-08-31 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Photochromic thermoplastic polyurethane elastomer material for waterproof moisture-permeable film and preparation method thereof |
CN112480653A (en) * | 2020-11-05 | 2021-03-12 | 苏州市雄林新材料科技有限公司 | Photochromic TPU (thermoplastic polyurethane) film for clothes and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102540721A (en) * | 2010-12-23 | 2012-07-04 | 比亚迪股份有限公司 | Photoresist composition and method for preparing fluorescent layer on surface of light emitting diode (LED) |
CN103930516A (en) * | 2011-12-26 | 2014-07-16 | 德山株式会社 | Photochromic composition |
CN104194321A (en) * | 2014-09-17 | 2014-12-10 | 朱忠良 | High temperature resistant TPU (thermoplastic polyurethanes) film and preparation method thereof |
CN106832213A (en) * | 2017-02-21 | 2017-06-13 | 东莞市雄林新材料科技股份有限公司 | A kind of Photosensitive TPU film and preparation method thereof |
-
2017
- 2017-06-30 CN CN201710520799.0A patent/CN107163223A/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102540721A (en) * | 2010-12-23 | 2012-07-04 | 比亚迪股份有限公司 | Photoresist composition and method for preparing fluorescent layer on surface of light emitting diode (LED) |
CN103930516A (en) * | 2011-12-26 | 2014-07-16 | 德山株式会社 | Photochromic composition |
CN104194321A (en) * | 2014-09-17 | 2014-12-10 | 朱忠良 | High temperature resistant TPU (thermoplastic polyurethanes) film and preparation method thereof |
CN106832213A (en) * | 2017-02-21 | 2017-06-13 | 东莞市雄林新材料科技股份有限公司 | A kind of Photosensitive TPU film and preparation method thereof |
Non-Patent Citations (3)
Title |
---|
刘凉冰: ""四氢呋喃均聚醚聚氨酯弹性体——影响PTMG-PU力学性能的因素"", 《化学推进剂与高分子材料》 * |
邝生鲁,等: "《现代精细化工 高新技术与产品合成工艺》", 31 December 1997, 科学技术文献出版社 * |
陈华辉 主编: "《耐磨材料应用手册》", 31 October 2012, 机械工业出版社 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109517120A (en) * | 2018-11-12 | 2019-03-26 | 安徽富瑞雪化工科技股份有限公司 | A kind of urethane acrylate discoloration lotion and preparation method |
CN111019166A (en) * | 2019-12-03 | 2020-04-17 | 东莞市雄林新材料科技股份有限公司 | TPU film with adjustable color opening and preparation method thereof |
CN111040422A (en) * | 2019-12-03 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Skin-feel TPU film and preparation method thereof |
CN111040425A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Polarity-adjustable TPU film and preparation method thereof |
CN111040423A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Electroluminescence color-changing TPU film and preparation method thereof |
CN111040424A (en) * | 2019-12-11 | 2020-04-21 | 东莞市雄林新材料科技股份有限公司 | Transparency-controllable TPU (thermoplastic polyurethane) film and preparation method thereof |
CN111040424B (en) * | 2019-12-11 | 2022-04-19 | 东莞市雄林新材料科技股份有限公司 | Transparency-controllable TPU (thermoplastic polyurethane) film and preparation method thereof |
CN112048053A (en) * | 2020-08-31 | 2020-12-08 | 山东一诺威聚氨酯股份有限公司 | Photochromic thermoplastic polyurethane elastomer material for waterproof moisture-permeable film and preparation method thereof |
CN112480653A (en) * | 2020-11-05 | 2021-03-12 | 苏州市雄林新材料科技有限公司 | Photochromic TPU (thermoplastic polyurethane) film for clothes and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107163223A (en) | A kind of photochromic TPU film of high temperature resistant and preparation method thereof | |
CN106832213A (en) | A kind of Photosensitive TPU film and preparation method thereof | |
CN105175678B (en) | A kind of high transparency polyurethane elastomer and preparation method thereof | |
US11226559B2 (en) | Blocking groups for light polymerizable resins useful in additive manufacturing | |
US7935422B2 (en) | Urethane polyol precursors for coating compositions | |
CN108530602B (en) | Color-changing polyurethane acrylic dye resin and preparation method thereof | |
CN110218290B (en) | Synthetic method of tough, transparent, fluorescent and antibacterial polyurethane film | |
CN106977682A (en) | A kind of U-shaped pillow super soft TPU film and preparation method thereof | |
CN112358844A (en) | Never-yellowing TPU (thermoplastic polyurethane) film glue for coating and preparation method and application thereof | |
CN111019510A (en) | Modified exposed single-component polyurethane waterproof coating and preparation method thereof | |
CN109912771A (en) | It is low that long-acting color inhibition thermoplastic polyurethane elastomer and preparation method thereof is precipitated | |
CN107652664A (en) | A kind of photosensitive colour-changing TPU film for adhering film to glass and preparation method thereof | |
CN108102065A (en) | Fiber reinforcement type thermoplastic polyurethane for bulletproof glass and preparation method thereof | |
CN108913000A (en) | A kind of water-repellent paint and preparation method | |
US4412022A (en) | Polyurethane coating compositions prepared from a polymeric diol, an alicyclic diisocyanate, an alicyclic diamine and either hydrazine or isophthalic acid dihydrazide | |
CN115322332B (en) | Fluorescent bio-based polyurethane capable of being self-repaired rapidly and preparation method thereof | |
CN110938301A (en) | TPU film for mobile phone film and preparation method thereof | |
CN109337355A (en) | A kind of high scratch resistance thermoplastic polyurethane elastomer and preparation method thereof | |
CN107089048B (en) | A kind of ice packet TPU composite material and preparation method | |
CN109456458A (en) | Polyether ester type TPU and preparation method thereof for footwear material | |
CN102584634B (en) | Polyurethane using vinyl ether as end group and synthesis method thereof | |
CN115322724A (en) | Environment-friendly high-low temperature impact-resistant weather-resistant bi-component polyurethane potting sealant and preparation method thereof | |
CN111234282A (en) | Aluminum-free high-brightness transfer film and preparation method thereof | |
CN113025031A (en) | Light-transmitting film and manufacturing method thereof | |
CN110835462B (en) | High-wear-resistance printable TPU film and preparation method thereof |
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 | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20170915 |
|
WW01 | Invention patent application withdrawn after publication |