CN105254866B - Carboxyl-terminated phosphorus-containing copolyester, preparation method, halogen-free flame retardant biology-based pressure sensitive adhesive composed of carboxyl-terminated phosphorus-containing copolyester and application - Google Patents
Carboxyl-terminated phosphorus-containing copolyester, preparation method, halogen-free flame retardant biology-based pressure sensitive adhesive composed of carboxyl-terminated phosphorus-containing copolyester and application Download PDFInfo
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- CN105254866B CN105254866B CN201510779872.7A CN201510779872A CN105254866B CN 105254866 B CN105254866 B CN 105254866B CN 201510779872 A CN201510779872 A CN 201510779872A CN 105254866 B CN105254866 B CN 105254866B
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Abstract
The invention discloses carboxyl-terminated phosphorus-containing copolyester which is formed by randomly connecting and combining structural units shown as I, II and III according to carboxyl and hydroxyl functional groups, and the Mw of the carboxyl-terminated phosphorus-containing copolyester is 1.1*10＜3＞-1.3*10＜4＞ g.mol＜-1＞. The invention further discloses a preparation method of the carboxyl-terminated phosphorus-containing copolyester, a halogen-free flame retardant biology-based pressure sensitive adhesive composed of the carboxyl-terminated phosphorus-containing copolyester and application. The copolyester is biology-based phosphorus-containing copolyester, the halogen-free flame retardant pressure sensitive adhesive formed by the copolyester and renewable resource epoxidized plant oil not only maintains the basic characteristics and good adhesive strength of a biology base, but also achieves the excellent halogen-free flame retardant properties, and the blank of biology-based halogen-free flame retardant pressure sensitive adhesive products is filled up; in addition, preparation is easy and mature, solvent is not used, the cost is low, pollution to the environment is little, and application and popularization are convenient.
Description
Technical field
The invention belongs to phosphorous copolyester and its preparation and pressure sensitive adhesive constitute technical field, and in particular to a kind of end carboxylic is biological
Base phosphorous copolyester and preparation method thereof and the halogen-free flameproof bio-based pressure sensitive adhesive being made from it and application.
Background technology
Pressure-sensitive adhesive (PSA), also referred to as " self-adhesive ", are a kind of tacky qualities and solid elastic for being provided simultaneously with liquid
The viscoelastic body of property.The viscoelastic body can be sticked to by viscous material list by non-covalent bond effect power under the effect of the pressure
Face, meanwhile, if destruction tack coat, the adhesive for coming off does not pollute adherend surface.Pressure sensitive adhesive be not typically used directly for by
The bonding of viscous thing, mainly makes the use of pressure sensitive adhesive product, such as adhesive tape and Adhesive Label etc. together with release paper with inertial base.
At present, polymeric pressure sensitive adhesive mainly includes acrylic copolymer, natural rubber, styrene-isoprene-phenylethene
Block copolymer (SBCs), styrene-butadiene-SBCs, SBR styrene butadiene rubberses and polysiloxanes etc..It can be seen that, except day
So outside the standby pressure sensitive adhesive of rubber system, the raw materials for production of most of pressure sensitive adhesive all rely on non-renewable petroleum resources, with stone
Gradually decreasing for oily resource, prepares renewable pressure sensitive adhesive using bio-based Renewable resource and increasingly receives publicity.From strategy storage
From the viewpoint of standby, using bio-based Renewable resource prepare pressure sensitive adhesive can not only reduce adhesives industry to petroleum resources according to
Rely, and the pollution to environment can also be reduced.
Vegetable oil is the abundant bio-based Renewable resource of a class, and which is by long-chain saturation or unsaturated fatty acid and glycerol
The native compound being bound up, the unsaturated double-bond in its long-chain fatty acid can also be transformed into easily by chemical reaction
The epoxide group for reacting.Though existing have document report anti-by condensation polymerization using the derivative binary acid of vegetable oil and dihydroxylic alcohols
The PEPA that should be obtained preparing pressure sensitive adhesive, however, in order to meet practical application, such polymer needs introducing crosslinked to tie
Adjusting its viscoelastic behavior, it is isocyanate ester compound that such as JP-2008-195819 discloses cross-linking agent of its introducing to structure, and
Isocyanate crosslinking has shortcomings, the toxicity problem for especially producing, and in base after prepared pressure-sensitive adhesive curing
Be also embodied by matter it is translucent, these all undoubtedly will limit respective pressure sensitive adhesive tape application.And for example WO 2011/
023255-A1 discloses a kind of polyester prepared with dimer (fatty acid) yl and dimeric fatty alcohol melt polycondensation, with epoxidized fatty acid
Ester prepares pressure sensitive adhesive and is further prepared into the method for pressure sensitive adhesive tape for cross-linking agent.Though pressure sensitive adhesive prepared by the method is also used
Organism-based raw material, meets Green Chemistry and sustainable development, and reduces the use of solvent, also more energy-conserving and environment-protective.But due to
Pressure sensitive adhesive product-use extensively, is related to the aspects such as daily life, commercial Application, export trade packaging, and different field is to pressure sensitive adhesive product
Performance requirement it is different, when pressure sensitive adhesive product application is in automobile, electrician trade, the prepared pressure sensitive adhesive product of special requirement will
With excellent anti-flammability, and the bio-based pressure sensitive adhesive product reported at present does not possess corresponding anti-flammability, especially Halogen
Anti-flammability.
The content of the invention
Present invention aims to the problem that prior art is present, provides a kind of end carboxyl phosphorous copolyester first,
The end carboxyl phosphorous copolyester is not only with biological based component as base material, and with excellent fire resistance.
The second object of the present invention is to provide a kind of method for preparing above-mentioned end carboxyl phosphorous copolyester.
The third object of the present invention is to provide a kind of halogen-free flameproof pressure sensitive adhesive being made up of above-mentioned end carboxyl phosphorous copolyester.
The fourth object of the present invention is to provide the application of above-mentioned halogen-free flameproof pressure sensitive adhesive.
The end carboxyl phosphorous copolyester that the present invention is provided, the copolyesters is the construction unit group represented by following I, II, III
Into：
X or Y [III]
When III construction units are-X-, III construction units number for II construction unit numbers 10～30%, [I+III's]
Construction unit number：Construction unit number=1.2～1.15 of II；When III construction units are-Y-, III construction units number is [II+
III] construction unit number 1～30%, the construction unit number of [I]：Construction unit number=1.2～1.15 of [II+III], it is each to tie
Structure unit or its segment for being formed are arbitrarily to connect combination by carboxyl and hydroxy functional group, and the end carboxyl phosphorous copolyester
1.1×103～1.3 × 104g·mol-1, wherein ,-the X- of III construction units is any one in following phosphor-containing structure：
- the Y- of III construction units is any one in following phosphor-containing structure：
Or
In formula, z=2,3,4,6 or 8.
In above phosphorous copolyester when III construction units are-X-, III construction units number for II construction unit numbers 20
～30%, the construction unit number of [I+III]：Construction unit number=1.2～1.15 of II；When III construction units are-Y-, III
Construction unit number for [II+III] construction unit number 20～30%, the construction unit number of [I]：The construction unit number of [II+III]
=1.2～1.15, and the 1.1 × 10 of the end carboxyl phosphorous copolyester3～1.3 × 104g·mol-1。
The method for preparing above-mentioned end carboxyl phosphorous copolyester that the present invention is provided, the method are by decanedioic acid, 1,2- the third two
Alcohol and A containing phosphorus component or B with total diacid in reaction raw materials and total diol molar ratio computing, by 1.1:1.0～2.0:1.0 add reaction
In container, then it is esterified using conventional direct esterification, after esterification terminates, is added the polycondensation of polyester of conventional proportions
Catalyst, then carry out polycondensation using conventional condensation methods and can be prepared by end carboxyl phosphorous copolyester,
The A containing phosphorus component or B for wherein adding is calculated as 10～30% with total diol mole percent in reaction raw materials, and phosphorous
Component A is any one in following phosphorous diacid：
B containing phosphorus component is any one in following phosphorous glycol：
Or
In formula, z=2,3,4,6 or 8.
The general structure of end carboxyl phosphorous copolyester prepared by above method is as follows：
Or
- X- in formula is remaining part after A containing phosphorus component reacted, and-Y- is remaining portion after B containing phosphorus component reacted
Point, m, n >=1 and be integer.
The A containing phosphorus component that adds in above method or B is preferably 20 with total diol mole percent in reaction raw materials～
30%.
In above method polyester polycondensation catalyst used be phosphoric acid, zinc acetate, manganese acetate, cobaltous acetate, antimony oxide,
Any one in antimony glycol or titanate esters.
The halogen-free flameproof pressure sensitive adhesive being made up of above-mentioned end carboxyl phosphorous copolyester that the present invention is provided, the halogen-free flameproof are pressure-sensitive
Glue is that 100 weight portion end carboxyl phosphorous copolyesters are warming up to 70～90 DEG C first, is subsequently adding 20～60 parts by weight epoxy plants
After oil and 1～5 weight portion curing catalysts are fully mixed, react 1～5 hour then at 130～170 DEG C.
In practical operation, should by the abundant liquid elder generation even spread for mixing on substrate surface after, then at 130～170
DEG C reaction 1～5 hour i.e. substrate surface formed halogen-free flameproof pressure sensitive adhesive.
The above-mentioned halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester, the halogen-free flameproof pressure sensitive adhesive are preferably added to
20～40 parts by weight epoxy vegetable oil and 1～4 weight portion curing catalysts.
The above-mentioned halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester, the halogen-free flameproof pressure sensitive adhesive more preferably add
Enter 20～30 parts by weight epoxy vegetable oil and 1～4 weight portion curing catalysts.
Epoxidized vegetable oil described in above halogen-free flameproof pressure sensitive adhesive is epoxy soybean oil, epoxy rapeseed oil, epoxy palm fibre paulownia
Oil, epoxy palm shell oil, epoxy castor oil, epoxy Semen Lini oil, epoxy coconut oil, epoxy cottonseed oil, epoxy olive oil or ring
Any one in oxygen sunflower oil, preferably epoxy soybean oil or epoxy Semen Lini oil, more preferably epoxy soybean oil.
Curing catalysts described in above halogen-free flameproof pressure sensitive adhesive be the preferred Nacure XC-258 in commercial catalyst,
Nacure XC-9206,2- ethyl imidazol(e) or praseodynium aluminum, more preferably catalyst n acure XC-258.
Base material described in above halogen-free flameproof pressure sensitive adhesive is dry goods, plastic sheeting class, foamed plastic class, paper tape and gold
Any one in category paper tinsel.Wherein dry goods base material is referred to by the blending of cotton yarn, polyester fiber, polypropylene fibre or acrylic fiber
The single fabric or union of yarn braiding；The plastic sheeting class base material is by PVC, Ρ Ε, PP, PI, EVA, PET or TPU
The thin film of preparation；The paper tape base material is flaxen fiber paper, kraft paper, crimped paper and cellophane；The metallic foil substrates are aluminium foil
Or Copper Foil.
Epoxidized vegetable oil described in the above halogen-free flameproof pressure sensitive adhesive press end carboxyl phosphorous copolyester mass fraction 20～
60% adds, and can obtain on steel plate 180 ° of peel strengths for 0.50～6.88N by base material one side coating pressure sensitive adhesive of PET
cm-1Fire retardant pressure sensitive adhesive tape；On polypropylene board, 180 ° of peel strengths are 0.23～3.32N cm-1Fire retardant pressure sensitive adhesive tape；
Limited oxygen index LOI is 20.5～26.0, and flammable UL-94 grades are VTM-2, and suspension method test flame resistance is 0 grade.
Epoxidized vegetable oil described in the above halogen-free flameproof pressure sensitive adhesive press end carboxyl phosphorous copolyester mass fraction 20～
40% adds, and can obtain on steel plate 180 ° of peel strengths for 0.80～6.88N by base material one side coating pressure sensitive adhesive of PET
cm-1Fire retardant pressure sensitive adhesive tape；On polypropylene board, 180 ° of peel strengths are 0.42～3.32N cm-1Fire retardant pressure sensitive adhesive tape；
LOI is VTM-2 for 20.5～26.0, UL-94, and suspension method test flame resistance is 0 grade.
Epoxidized vegetable oil described in the above halogen-free flameproof pressure sensitive adhesive press end carboxyl phosphorous copolyester mass fraction 20～
30% adds, and can obtain on steel plate 180 ° of peel strengths for 3.42～6.88N by base material one side coating pressure sensitive adhesive of PET
cm-1Fire retardant pressure sensitive adhesive tape；On polypropylene board, 180 ° of peel strengths are 2.09～3.32N cm-1Fire retardant pressure sensitive adhesive tape；
LOI is VTM-2 for 20.5～26.0, UL-94, and suspension method test flame resistance is 0 grade.
Epoxidized vegetable oil described in the above halogen-free flameproof pressure sensitive adhesive press end carboxyl phosphorous copolyester mass fraction 20～
60% adds, and can obtain on steel plate 180 ° of peel strengths for 0.47～6.68N cm by base material one side coating pressure sensitive adhesive of PI-1
Fire retardant pressure sensitive adhesive tape；On polypropylene board, 180 ° of peel strengths are 0.22～5.62N cm-1Fire retardant pressure sensitive adhesive tape；LOI is
30.0～40.0, UL-94 are VTM-0, and suspension method test flame resistance is 0 grade.
Epoxidized vegetable oil described in the above halogen-free flameproof pressure sensitive adhesive press end carboxyl phosphorous copolyester mass fraction 20～
40% adds, and can obtain on steel plate 180 ° of peel strengths for 1.44～6.88N cm by base material one side coating pressure sensitive adhesive of PI-1
Fire retardant pressure sensitive adhesive tape；On polypropylene board, 180 ° of peel strengths are 0.42～3.32N cm-1Fire retardant pressure sensitive adhesive tape；LOI is
30.0～40.0, UL-94 are VTM-0, and suspension method test flame resistance is 0 grade.
Epoxidized vegetable oil described in the above halogen-free flameproof pressure sensitive adhesive press end carboxyl phosphorous copolyester mass fraction 20～
30% adds, and can obtain on steel plate 180 ° of peel strengths for 3.64～6.88N cm by base material one side coating pressure sensitive adhesive of PI-1
Fire retardant pressure sensitive adhesive tape；On polypropylene board, 180 ° of peel strengths are 0.42～3.32N cm-1Fire retardant pressure sensitive adhesive tape；LOI is
30.0～40.0, UL-94 are VTM-0, and suspension method test flame resistance is 0 grade.
The application of the halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester that the present invention is provided is in adhesive tape, mark
Application in label, the processing of packaging, bookbinding, surface protection film, timber, wallpaper or electrician's articles for use.
The present invention compared with prior art, has the positive effect that：
1st, as the end carboxyl phosphorous copolyester of present invention offer is in addition to phosphorous-containing monomers, diacid and glycol all can be by bio-based
Prepare, and polymerization is also adopted by polymerisation in bulk, does not use solvent, thus not only makes the acquisition of the end carboxyl phosphorous copolyester
Not exclusively rely on petroleum resources, and become a kind of new bio-based phosphorous copolyester, and can reduces cost, reduce the dirt to environment
Dye.
2nd, it is phosphorous in the end carboxyl copolyesters provided due to the present invention, and and directly can react with epoxide group,
Thus which can not only be used for preparing the base material of biological fundamental mode pressure sensitive adhesive, can give prepared biological fundamental mode pressure sensitive adhesive excellent nothing again
Halogen fire-retardancy, kills two birds with one stone.
3rd, due to the present invention provide halogen-free flameproof pressure sensitive adhesive except its base material be adopt biological fundamental mode end carboxyl it is phosphorous
Copolyesters, cure-crosslinking agent are also that using Renewable resource epoxidized vegetable oil, the preparation process of pressure sensitive adhesive does not use molten yet in addition
Agent, thus on the one hand make the pressure sensitive adhesive of acquisition both keep the fundamental characteristics of bio-based, on the other hand obtain the pressure sensitive adhesive of acquisition again
The characteristic of halogen-free flameproof was obtained, and had also filled up the blank of bio-based halogen-free flameproof pressure sensitive adhesive product.
4th, as the bio-based halogen-free flameproof pressure sensitive adhesive that the present invention is provided belongs to pressure sensitive adhesive ingrain fireproofing, thus it is on the one hand right
Pressure sensitive adhesive product is prepared, the especially selection of the inert base of pressure sensitive adhesive tape is not limited, applied widely, it is on the other hand elected
When selecting the inert base of pressure sensitive adhesive tape and also having certain anti-flammability, the anti-flammability of the pressure sensitive adhesive tape will be very outstanding, and it is right to can be used for
The higher field of flame-retardancy requirements.
5th, the composition of the bio-based halogen-free flameproof pressure sensitive adhesive provided due to the present invention is simple, and need not additionally add thickening
Resin can just reach good bonding force, and fire resistance is again good, the adhesive strength and electrical property on adhesive tape substantially without impact,
Thus can be widely used for the fields such as building materials, electronics, automobile inner decoration facing bonding.
6th, the preparation method that the present invention is provided is simple, ripe, and preparation process is routine operation, easy to utilize.
Description of the drawings
Fig. 1 is the core of the phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl prepared by the embodiment of the present invention 3
Magnetic resonance hydrogen spectrogram.In figure, 12.0ppm is the chemical shift of the hydrogen on carboxyl, illustrates that the copolyesters contains end carboxyl, 6.8～
Chemical shifts of the 8.2ppm for phosphor-containing structure group benzene ring hydrogen, illustrates phosphorus-containing groups DOPOHQHE are introduced copolyesters successfully
In.
Fig. 2 is the core of the phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl prepared by the embodiment of the present invention 8
Magnetic resonance hydrogen spectrogram.In figure, 12.0ppm is the chemical shift of the hydrogen on carboxyl, illustrates that the copolyesters contains end carboxyl, 7.1～
8.2ppm is the chemical shift of phosphor-containing structure group benzene ring hydrogen, illustrates successfully phosphorus-containing groups DDP are introduced in copolyesters.
Specific embodiment
The present invention is specifically described below by embodiment, what deserves to be explained is following examples are intended merely to this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in the field according to
The invention described above content makes some nonessential modifications and adaptations to the present invention, still falls within protection scope of the present invention.
What deserves to be explained is, the 1) weight average molecular weight tested by end carboxyl phosphor-containing flame-retardant copolyester prepared by following examples
Mw is using the test of gel chromatography GPC.2) the limited oxygen index LOI of the phosphor-containing flame-proof pressure sensitive adhesive tape for preparing in following examples is
Tested according to the program of GB/T 2406-1993 using HC-2C types oxygen index measurer；Vertical combustion UL-94 is to adopt
CZF-2 types Vertical combustion instrument is tested according to the test program of GB/T 2408-1996；Suspension method anti-flammability is by GB/
T15903-1995 standards are carried out, and are divided into 0 (not firing), 1 (self-extinguishment, flame resistance are preferable), 2 (flammable, flame resistance is poor), 3 (flammable)
Four grades；180 ° of peel strengths are carried out by GB/T2792-1998 standards.
Embodiment 1
By 209.3g (1.04mol) decanedioic acid, 76.1g (1.00mol) 1,2- Propylene Glycol and 34.6g DDP (0.10mol)
In adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml butyl titanate toluene
Solution (0.2g ml-1), and solution is heated to into 220 DEG C, and coarse vacuum polycondensation 0.5h, it is phosphorous that fine vacuum polycondensation 4h obtains final product end carboxyl
Poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters.
The M of the copolyesterswFor 5.9 × 103g·mol-1。
Embodiment 2
By 202.2g (1.00mol) decanedioic acid, 76.1g (1.00mol) 1,2- Propylene Glycol and 51.9g DDP (0.15mol)
In adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml butyl titanate toluene
Solution (0.2g ml-1), and solution is heated to into 220 DEG C, and coarse vacuum polycondensation 0.5h, it is phosphorous that fine vacuum polycondensation 4h obtains final product end carboxyl
Poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters.
The M of the copolyesterswFor 7.0 × 103g·mol-1。
Embodiment 3
By 186.0g (0.92mol) decanedioic acid, 76.1g (0.10mol) 1,2- Propylene Glycol and 69.3g DDP (0.20mol)
In adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml butyl titanate toluene
Solution (0.2g ml-1), and solution is heated to into 220 DEG C, and coarse vacuum polycondensation 0.5h, it is phosphorous that fine vacuum polycondensation 4h obtains final product end carboxyl
Poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters.
The M of the copolyesterswFor 7.5 × 103g·mol-1。
Embodiment 4
By 192.1g (0.95mol) decanedioic acid, 76.1g (0.10mol) 1,2- Propylene Glycol and 86.6g DDP (0.25mol)
In adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml butyl titanate toluene
Solution (0.2g ml-1), and solution is heated to into 220 DEG C, and coarse vacuum polycondensation 0.5h, it is phosphorous that fine vacuum polycondensation 4h obtains final product end carboxyl
Poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters.
The M of the copolyesterswFor 8.0 × 103g·mol-1。
Embodiment 5
By 32.4g DOPO-HQ, 26.4g ethylene carbonates, 50g N, N '-dimethyl acetamide and 0.4g catalyst iodate
Potassium is added in reaction vessel, by oil bath heating to 160 DEG C under nitrogen protection, while opening stirring；When reaction is carried out to anti-
Answer after substantially no bubble is emerged in fused mass in container and stop, reacting overall process about 8h；Solution is slowly dripped after being down to room temperature
Enter in a certain amount of water, while being stirred vigorously, to powder precipitation is produced, product is washed twice by sucking filtration with a small amount of methanol, 45 DEG C
White powdery solids DOPOHQHE is obtained after lower drying.
By 232.5g (1.15mol) decanedioic acid, 68.5g (0.90mol) 1,2- Propylene Glycol and 41.2g DOPOHQHE
(0.10mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 7.5 × 103g·mol-1。
Embodiment 6
By 232.5g (1.15mol) decanedioic acid, 60.9g (0.80mol) 1,2- Propylene Glycol and 82.4g DOPOHQHE
(0.20mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 7.0 × 103g·mol-1。
Embodiment 7
By 232.5g (1.15mol) decanedioic acid, 57.1g (0.75mol) 1,2- Propylene Glycol and 103.0g DOPOHQHE
(0.25mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 6.6 × 103g·mol-1。
Embodiment 8
By 232.5g (1.15mol) decanedioic acid, 53.3g (0.70mol) 1,2- Propylene Glycol and 123.6g DOPOHQHE
(0.30mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 6.8 × 103g·mol-1。
Embodiment 9
By 232.5g (1.15mol) decanedioic acid, 57.1g (0.75mol) 1,2- Propylene Glycol and 93.8g DOPO-HHAM
(0.25mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 6.9 × 103g·mol-1。
Embodiment 10
By 232.5g (1.15mol) decanedioic acid, 53.3g (0.70mol) 1,2- Propylene Glycol and 112.5g DOPO-HHAM
(0.30mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 7.7 × 103g·mol-1。
Embodiment 11
By 186.0g (0.92mol) decanedioic acid, 76.1g (1.00mol) 1,2- Propylene Glycol and 66.5g DOPO-MA
(0.20mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 7.5 × 103g·mol-1。
Embodiment 12
By 232.5g (1.15mol) decanedioic acid, 57.1g (0.75mol) 1,2- Propylene Glycol and 97.3g DOPO-BHAM
(0.25mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 7.8 × 103g·mol-1。
Embodiment 13
By 232.5g (1.15mol) decanedioic acid, 57.1g (0.75mol) 1,2- Propylene Glycol and 116.0g DOPO-NQ
(0.25mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 1.2 × 104g·mol-1。
Embodiment 14
By 232.5g (1.15mol) decanedioic acid, 60.9g (0.80mol) 1,2- Propylene Glycol and 119.2g DOPO-TPE
(0.20mol) in adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml metatitanic acids
Four butyl ester toluene solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 4h are obtained final product
The phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters of end carboxyl.
The M of the copolyesterswFor 1.3 × 104g·mol-1。
Embodiment 15
By 192.1g (0.95mol) decanedioic acid, 76.1g (0.10mol) 1,2- Propylene Glycol and 86.6g DDP (0.25mol)
In adding reaction vessel, then under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml butyl titanate toluene
Solution (0.2g ml-1), and solution is heated to into 220 DEG C, coarse vacuum polycondensation 0.5h, fine vacuum polycondensation 0.5h obtain final product end carboxyl
Phosphorous poly- decanedioic acid -1,2- propylene glycol ester flame-proof copolyesters
The M of the copolyesterswFor 1.1 × 103g·mol-1。
Embodiment 16～20
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 3 are warming up to into 80 DEG C, weight in table 1 is subsequently adding
After part epoxy soybean oil and curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on thickness with scraper is
0.05mm, width, 3 hours can systems then at 160 DEG C of reactions for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness
Obtain halogen-free flameproof pressure sensitive adhesive tape.
Table 1
Embodiment 21
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 4 are warming up to into 80 DEG C, 30 weight portion rings are subsequently adding
After oxygen soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
For 0.05mm, width is for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, is reacted 3 hours then at 160 DEG C
Prepared halogen-free flameproof pressure sensitive adhesive tape.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 6.35 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 3.31 ± 0.25N cm-1；It is VTM-2 that LOI is 27.5, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 22
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 3 are warming up to into 80 DEG C, 30 weight portion rings are subsequently adding
After oxygen soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
For 0.05mm, width is for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, is reacted 2 hours then at 170 DEG C
Prepared halogen-free flameproof pressure sensitive adhesive tape.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 5.15 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 2.21 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 23
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 3 are warming up to into 80 DEG C, 30 weight portion rings are subsequently adding
After oxygen soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
For 0.05mm, width is for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, is reacted 5 hours then at 130 DEG C
Prepared halogen-free flameproof pressure sensitive adhesive tape.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 5.55 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 2.21 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 24
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 3 are warming up to into 70 DEG C, 30 weight portion rings are subsequently adding
After oxygen soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
For 0.05mm, width is for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, is reacted 4 hours then at 150 DEG C
Prepared halogen-free flameproof pressure sensitive adhesive tape.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 5.25 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 2.41 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 25～28
The proportioning of end carboxyl phosphorous copolyester according to the form below 2 prepared by embodiment 8, is prepared using the condition of embodiment 16
The correlated performance of halogen-free flameproof pressure sensitive adhesive tape see the table below 2.Wherein catalyst uses Nacure XC-258
Table 2
Embodiment 29
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 8 are warming up to into 70 DEG C, 30 weight portion rings are subsequently adding
After oxygen soybean oil and 3 weight portion curing catalysts Nacure XC-9206 are fully mixed, liquid is uniformly coated on into thickness with scraper
Spend for 0.05mm, width for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, then at 150 DEG C of reactions 4 hours i.e.
Halogen-free flameproof pressure sensitive adhesive tape can be obtained.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 6.48 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 2.83 ± 0.17N cm-1；It is VTM-2 that LOI is 25.5, UL-94, suspension method 1 grade of flame resistance of test.
Embodiment 30
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 3 are warming up to into 70 DEG C, 30 weight portion rings are subsequently adding
After oxygen soybean oil and 3 weight portion curing catalysts Nacure XC-9206 are fully mixed, liquid is uniformly coated on into thickness with scraper
Spend for 0.05mm, width for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, then at 150 DEG C of reactions 4 hours i.e.
Halogen-free flameproof pressure sensitive adhesive tape can be obtained.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 5.05 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 2.01 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 31～33
The proportioning of end carboxyl phosphorous copolyester according to the form below 3 prepared by embodiment 10, is prepared using the condition of embodiment 16
The correlated performance of halogen-free flameproof pressure sensitive adhesive tape see the table below 3.Wherein catalyst uses Nacure XC-258.
Table 3
Embodiment 34
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 11 are warming up to into 80 DEG C, 30 weight portions are subsequently adding
After epoxy soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
Spend for 0.05mm, width for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, then at 130 DEG C of reactions 5 hours i.e.
Halogen-free flameproof pressure sensitive adhesive tape can be obtained.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 5.15 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 2.21 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 35
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 12 are warming up to into 80 DEG C, 30 weight portions are subsequently adding
After epoxy soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
Spend for 0.05mm, width for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, then at 160 DEG C of reactions 3 hours i.e.
Halogen-free flameproof pressure sensitive adhesive tape can be obtained.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 6.15 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 3.21 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 36
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 13 are warming up to into 80 DEG C, 30 weight portions are subsequently adding
After epoxy soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
Spend for 0.05mm, width for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, then at 160 DEG C of reactions 3 hours i.e.
Halogen-free flameproof pressure sensitive adhesive tape can be obtained.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 6.05 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 3.21 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 37
100 weight portion end carboxyl phosphorous copolyesters prepared by embodiment 14 are warming up to into 80 DEG C, 30 weight portions are subsequently adding
After epoxy soybean oil and 3 weight portion curing catalysts Nacure XC-258 are fully mixed, liquid is uniformly coated on into thickness with scraper
Spend for 0.05mm, width for, on the PET mylars of 1000mm, it is 0.025mm that glue applies thickness, then at 160 DEG C of reactions 3 hours i.e.
Halogen-free flameproof pressure sensitive adhesive tape can be obtained.
Gained halogen-free flameproof pressure sensitive adhesive tape 180 ° of peel strengths on steel plate are 6.25 ± 0.5N cm-1；In polypropylene board
Upper 180 ° of peel strengths are 3.01 ± 0.25N cm-1；It is VTM-2 that LOI is 26.0, UL-94, suspension method 0 grade of flame resistance of test.
Embodiment 38～40
The proportioning of end carboxyl phosphorous copolyester, epoxy Semen Lini oil and catalyst according to the form below 4 prepared by embodiment 3, adopts
The correlated performance of the halogen-free flameproof pressure sensitive adhesive tape prepared with the condition of embodiment 16 see the table below 4.Wherein catalyst is used
Nacure XC-258。
Table 4
Embodiment 41～46
The proportioning of end carboxyl phosphorous copolyester, epoxy soybean oil and catalyst according to the form below 5 prepared by embodiment 1,70
After DEG C stirring 0.5h obtains homogeneous liquid, it is 0.05mm that liquid is uniformly coated on thickness with scraper, and width is the poly- of 1000mm
In polyimide PI film, it is 0.025mm that glue applies thickness, can be prepared by halogen-free flameproof pressure sensitive adhesive tape, gained then at 160 DEG C of reaction 3h
The correlated performance of halogen-free flameproof pressure sensitive adhesive tape see the table below 5.Wherein catalyst uses Nacure XC-258.
Table 5
Embodiment 47～52
The proportioning of end carboxyl phosphorous copolyester, epoxy soybean oil and catalyst according to the form below 6 prepared by embodiment 3, adopts
The correlated performance of halogen-free flameproof pressure sensitive adhesive tape prepared by the condition of embodiment 41 see the table below 6.Wherein catalyst is used
Nacure XC-258。
Table 6
Embodiment 53～56
The proportioning of end carboxyl phosphorous copolyester, epoxy soybean oil and catalyst according to the form below 7 prepared by embodiment 8, adopts
The correlated performance of halogen-free flameproof pressure sensitive adhesive tape prepared by the condition of embodiment 41 see the table below 7.Wherein catalyst is used
Nacure XC-258。
Table 7
Embodiment 57～59
The proportioning of end carboxyl phosphorous copolyester, epoxy Semen Lini oil and catalyst according to the form below 8 prepared by embodiment 10, adopts
The correlated performance of the halogen-free flameproof pressure sensitive adhesive tape prepared with the condition of embodiment 41 see the table below 8.Wherein catalyst is used
Nacure XC-258。
Table 8
Embodiment 60～63
The proportioning of end carboxyl phosphorous copolyester, epoxy soybean oil and catalyst according to the form below 9 prepared by embodiment 15, adopts
The correlated performance of halogen-free flameproof pressure sensitive adhesive tape prepared by the condition of embodiment 41 see the table below 9.Wherein catalyst is used
Nacure XC-258。
Table 9
Comparative example 1～5
232.5g (1.15mol) decanedioic acid, 76.1g (1.00mol) 1,2-PD are added in reaction vessel, Ran Hou
Under nitrogen protection, esterification 4h is stirred in 180 DEG C, add 0.1ml butyl titanate toluene solution (0.2g ml-1), and will
Solution is heated to 220 DEG C, coarse vacuum polycondensation 0.5h, and fine vacuum polycondensation 4h obtains final product the poly- decanedioic acid of end carboxyl -1,2-PD ester altogether
Polyester.
The M of the copolyesterswFor 4.9 × 103g·mol-1。
Poly- decanedioic acid -1,2- propylene glycol esters the copolyesters of end carboxyl, epoxy soybean oil and catalyst prepared by by more than is pressed
The proportioning of table 9 below, the correlated performance of the pressure sensitive adhesive tape prepared using the condition of embodiment 16 see the table below 10.Wherein catalyst is adopted
Be Nacure XC-258.
Table 10
Comparative example 6～10
By the poly- decanedioic acid -1,2- propylene glycol esters copolyesters of end carboxyl obtained by above comparative example, epoxy soybean oil and catalysis
The proportioning of agent according to the form below 10, the correlated performance of the pressure sensitive adhesive tape prepared using the condition of embodiment 41 see the table below 11.Wherein it is catalyzed
Agent uses Nacure XC-258.
Table 11
Claims (6)
1. a kind of halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester, the halogen-free flameproof pressure sensitive adhesive is first by 100 weights
Amount part end carboxyl phosphorous copolyester is warming up to 70～90 DEG C, is subsequently adding 20～60 parts by weight epoxy vegetable oil and 1～5 weight portion
After curing catalysts are fully mixed, react 1～5 hour then at 130～170 DEG C, the phosphorous copolymerization of wherein described end carboxyl
Ester is made up of the construction unit that following I, II, III are represented：
X or Y [III]
When III construction units are-X-, III construction units number for II construction unit numbers 10～30%, the structure of [I+III]
Unit number：Construction unit number=1.2～1.15 of II；When III construction units are-Y-, III construction units number is [II+III]
The 1～30% of construction unit number, the construction unit number of [I]：Construction unit number=1.2～1.15 of [II+III], each structure list
Unit or its segment for being formed are arbitrarily to connect combination by carboxyl and hydroxy functional group, and the Mw of the end carboxyl phosphorous copolyester is
1.1×103～1.3 × 104g·mol-1, wherein ,-the X- of III construction units is any one in following phosphor-containing structure：
- the Y- of III construction units is any one in following phosphor-containing structure：
In formula, z=2,3,4,6 or 8.
2. the halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester according to claim 1, the halogen-free flameproof pressure
In end carboxyl phosphorous copolyester described in quick glue when III construction units are-X-, III construction units number is II construction units
Several 20～30%, the construction unit number of [I+III]：Construction unit number=1.2～1.15 of II；When III construction units are-Y-
When, III construction units number for [II+III] construction unit number 20～30%, the construction unit number of [I]：The structure of [II+III]
Unit number=1.2～1.15, and the Mw of the end carboxyl phosphorous copolyester is 1.1 × 103～1.3 × 104g·mol-1。
3. the halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester according to claim 1 and 2, the halogen-free flameproof
Epoxidized vegetable oil described in pressure sensitive adhesive is epoxy soybean oil, epoxy rapeseed oil, epoxy brown tung oil, epoxy palm shell oil, epoxy
Any one in Oleum Ricini, epoxy Semen Lini oil, epoxy coconut oil, epoxy cottonseed oil, epoxy olive oil or epoxy sunflower oil.
4. the halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester according to claim 1 and 2, the halogen-free flameproof
Curing catalysts described in pressure sensitive adhesive be commercial catalyst Nacure XC-258, Nacure XC-9206,2- ethyl imidazol(e)s or
Praseodynium aluminum.
5. the halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester according to claim 3, the halogen-free flameproof pressure
Curing catalysts described in quick glue are commercial catalyst Nacure XC-258, Nacure XC-9206,2- ethyl imidazol(e)s or three
Aluminium acetylacetonate.
6. the halogen-free flameproof pressure sensitive adhesive being made up of end carboxyl phosphorous copolyester described in a kind of claim 1 is in adhesive tape, label, bag
Application in dress, bookbinding, surface protection film, timber processing, wallpaper or electrician's articles for use.
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| CN110885345B (en) | 2018-09-11 | 2022-06-28 | 财团法人工业技术研究院 | Secondary amines, free radicals, and alkoxyamine compounds |
| CN113045741B (en) * | 2019-12-26 | 2023-06-30 | 洛阳尖端技术研究院 | Phosphorus-containing carboxyl-terminated hyperbranched polyester, preparation method thereof, phosphorus-containing hyperbranched epoxy resin, preparation method thereof and application thereof |
| CN113416284B (en) * | 2021-05-25 | 2022-06-24 | 华南农业大学 | Vegetable oil-based halogen-free flame-retardant epoxy acrylate and preparation method and application thereof |
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| CN101307139A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | Method for synthesizing phosphorus-containing polyester for fire retardant electronic packaging material |
| CN101314636A (en) * | 2007-05-31 | 2008-12-03 | 中国科学院化学研究所 | Biodegradable aliphat dibasic acid 1,2-propylene glycol ester and copolyester, and preparation thereof |
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| CN101307139A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | Method for synthesizing phosphorus-containing polyester for fire retardant electronic packaging material |
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