CN106633012A - Polyester resin for heat transfer printing powder coating and preparation method of polyester resin - Google Patents
Polyester resin for heat transfer printing powder coating and preparation method of polyester resin Download PDFInfo
- Publication number
- CN106633012A CN106633012A CN201611269928.5A CN201611269928A CN106633012A CN 106633012 A CN106633012 A CN 106633012A CN 201611269928 A CN201611269928 A CN 201611269928A CN 106633012 A CN106633012 A CN 106633012A
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- Prior art keywords
- polyester resin
- acid
- antioxidant
- added
- 35mgkoh
- Prior art date
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 36
- 239000004645 polyester resin Substances 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000010023 transfer printing Methods 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 12
- 238000005886 esterification reaction Methods 0.000 claims description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 10
- 239000001361 adipic acid Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- -1 hydroxycarboxyl group Chemical group 0.000 claims description 10
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- USEBIPUIVPERGC-UHFFFAOYSA-N Dibutylone Chemical compound CCC(N(C)C)C(=O)C1=CC=C2OCOC2=C1 USEBIPUIVPERGC-UHFFFAOYSA-N 0.000 claims 1
- RIWQWHDNZIGXOI-UHFFFAOYSA-M [P].[Br-].C1(=CC=CC=C1)[P+](CC)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[Br-].C1(=CC=CC=C1)[P+](CC)(C1=CC=CC=C1)C1=CC=CC=C1 RIWQWHDNZIGXOI-UHFFFAOYSA-M 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- BYSFLEQBDOJVAR-UHFFFAOYSA-L dibutyltin(2+);dihydroxide Chemical compound [OH-].[OH-].CCCC[Sn+2]CCCC BYSFLEQBDOJVAR-UHFFFAOYSA-L 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 13
- 230000008018 melting Effects 0.000 abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 30
- 239000000178 monomer Substances 0.000 description 10
- 239000003973 paint Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OBRRAKVAHFFXFF-UHFFFAOYSA-N 2-phenylethylphosphanium;bromide Chemical compound [Br-].[PH3+]CCC1=CC=CC=C1 OBRRAKVAHFFXFF-UHFFFAOYSA-N 0.000 description 1
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012374 esterification agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a polyester resin for a heat transfer printing powder coating and a preparation method of the polyester resin. The polyester resin has hydroxyl and carboxyl bifunctional groups, has the acid value of 25-35mgKOH/g, the hydroxyl value of 25-35mgKOH/g, the crystallinity degree of 0-85%, the melting point of 120-180 DEG C, the melt viscosity of 10-100Pa.s at the temperature of 160 DEG C and the number-average molecular weight of 3000-5000, and is characterized by being prepared from the following raw materials in percentage by weight through melt phase polycondensation, wherein the structural formula is shown in the specification.
Description
The present invention relates to a kind of thermal transfer hydroxycarboxyl group difunctional polyester resin used for powder coating and preparation method thereof.With
Common monohydroxy is compared with the polyester of mono carboxylic polyester resin or the physical mixed of two kinds of polyester resin, presently disclosed
Polyester resin, with more preferable levelling and while mechanical performance, with more preferable thermal transfer effect.
CN 101704945B disclose a kind of mixed type thermal transfer polyester resin for powder coating and preparation method thereof, should
Mixed type thermal transfer polyester resin for powder coating includes following components and content：The mol ratio of acid/alcohol is 1/ in polyester resin
1.05-1.20；The percentage ratio that wherein content of each alcohol accounts for respectively total alcohol molal quantity is：Neopentyl glycol 10-90mol%；2 methyl
1,3 Propylene Glycol 0-45mol%；Ethylene glycol 0-20mol%；Diethylene glycol 10-25mol%；Wherein each sour content is accounted for respectively always
The percentage ratio of sour molal quantity is：P-phthalic acid 80-100mol%；M-phthalic acid 0-10mol%；Adipic acid 0-10mol%；
Trimellitic anhydride accounts for the 10-15wt% of polyester resin total amount；The salt of compounding accounts for the 0.1-1.0wt% of polyester resin total amount,
Adjusting the degree of functionality of polyester resin, the cured film of gained has the amount by trimellitic anhydride branched component of the polyester resin
More preferable appearance, and realize (160 DEG C) solidifications of low temperature, and film low-temperature solid rate is high, cured film has good resistance to
Solvent nature, the clear true to nature and easy paper-tear picture of the transfer film after transfer.
CN 102666644B disclose it is a kind of comprising the monomeric unit derived from di-or polyfunctional organic acid compound A and
The polyester AB of the monomeric unit derived from di-or polyfunctional organic hydroxy compounds B, wherein the compound A has comprising per molecule
There are " hard " the acid compound A1 and soft acid compound A2 of two or more acidic groups, the compound B has two comprising per molecule
Or " hard " the hydroxy functional compound B1 and soft hydroxy functional compound B2 of multiple hydroxyls, and by them and selected from Carbimide.
Coating material composition prepared by the cross-linking agent of the group of ester, blocked isocyanate, aminoplast crosslinking agent and phenolast cross-linker composition
Thing, and their applications in metal base coating.
The invention provides a kind of thermal transfer hydroxycarboxyl group difunctional polyester resin used for powder coating, it is characterised in that
The hydroxyl value of the acid number with 25-35mgKOH/g and 25-35mgKOH/g, degree of crystallinity 0-85%, fusing point is 120-180 DEG C, 160 DEG C
Melt viscosity in 10-100Pa.s, number-average molecular weight is melted in 3000-5000 or so by the raw material Jing of following percentage by weight
Polycondensation reaction is obtained：
Polyol component neopentyl glycol 30-50wt%
Ethylene glycol 0-10wt%
Trimethylolpropane 0-10wt%
Polyacid component p-phthalic acid 50-70wt%,
M-phthalic acid 0-10wt%
Adipic acid 0-10%
Acidolysis agent trimellitic anhydride 0-10wt%
Esterification catalyst 0-0.1wt%.
The invention provides a kind of thermal transfer hydroxycarboxyl group difunctional polyester resin used for powder coating, is prepared by following methods,
1) polyol component neopentyl glycol 30-50wt% is added
Ethylene glycol 0-10wt%
Trimethylolpropane 0-10wt%
With esterification catalyst component 0-0.1wt%, antioxidant G (0-0.1wt%) is gradually heating to while stirring its complete
Full-fusing；
2) polyacid component p-phthalic acid 50-70wt% is added,
M-phthalic acid 0-10wt%
Adipic acid 0-10wt%
Being warmed up to 240-260 DEG C carries out esterification；Until system acid number is less than 15mgKOH/g；
3) 220-230 DEG C is cooled to, progressively evacuation polycondensation, vacuum is 40-50mbar, reacts 1-3 hours, acid number is little
In 10mgKOH/g, hydroxyl value is in 40-50mgKOH/g；
4) 150-160 DEG C is cooled to, acidolysis agent trimellitic anhydride 0-10wt% is added, 2-5 hours are reacted, and adjusts body
It is acid number to 25-35mgKOH/g, hydroxyl value to 25-35mgKOH/g；
5) after reaction terminates, antioxidant H (0-0.1wt%) and curing accelerator (0-0.5wt%) are added, stirs 20-30
Resin can discharge after minute is uniform, and cooling crush is standby；Relative to the gross weight for all feeding intake.
Preferably, the polyester resin has the degree of crystallinity of 0-85%, more preferably 1-50%, most preferably 2-
20%.
Preferably, the polyester resin has 120-180 DEG C of fusing point, more preferably 125-170 DEG C, most preferably
140-160℃。
Preferably, the polyester resin is 10-100Pa.s in the melt viscosity with 160 DEG C, more preferably 15-
80Pa.s, most preferably 20-50Pa.s.
Preferably, neopentyl glycol content is 30-50wt% in the polyol, more preferably 40-50wt%, most
Preferably 40-45wt%；
Preferably, ethylene glycol content is 0-10wt% in the polyol, more preferably 1-5wt%, most preferably
Ground is 1-3wt%；
Preferably, trimethylolpropane content is 0-10wt% in the polyol, more preferably 5-10wt%,
Most preferably 5-8wt%；
Preferably, terephthaldehyde's acid content is 50-70wt% in the polyacid component, more preferably 50-60wt%,
Most preferably 55-60wt%；
Preferably, M-phthalic acid content is 0-10wt% in the polyacid component, more preferably 1-8wt%, most
Preferably 2-5wt%；
Preferably, adipic acid content is 0-10wt% in the middle of the polyacid component, more preferably 1-8wt%, optimum
Selection of land is 2-5wt%；
Preferably, the acidolysis agent trimellitic anhydride content is 0-10wt%, more preferably 5-10wt%, most preferably
For 5-8wt%；
Preferably, the catalyzing esterification agent content is 0-0.1wt%, more preferably 0.01-0.05wt%, most preferably
For 0.01-0.02wt%
Described polyester resin has the acid number of 25-35mgKOH/g and the hydroxyl value of 25-35mgKOH/g.
Preferably, described polyester resin has the acid number of 28-32mgKOH/g and the hydroxyl value of 28-32mgKOH/g；It is more excellent
Selection of land, described polyester resin has the acid number of 29-31mgKOH/g and the hydroxyl value of 29-31mgKOH/g.
Described esterification catalyst is preferably tin catalyst, selected from Dibutyltin oxide, tributyltin oxide, dihydroxy fourth
Base stannic chloride, one or several in stannous oxalate.
Described curing accelerator can be selected from tetraethylammonium bromide, 4 bromide, benzyltriethylammoinium chloride, three
One or more in phenylethyl phosphonium bromide.
Described antioxidant G and antioxidant H can be same or different antioxidant, and the antioxidant is selected from hindered phenol
The combination of class primary antioxidant and phosphorous acid esters auxiliary antioxidant.
Present invention also offers a kind of prepare the method that thermal transfer hydroxycarboxyl group dual intensity used for powder coating rolls into a ball polyester resin, bag
Containing following steps：
1) polyol component neopentyl glycol 30-50wt% is added
Ethylene glycol 0-10wt%
Trimethylolpropane 0-10wt%
With, esterification catalyst component 0-0.1wt%, 140-160 DEG C is gradually heating to while stirring makes it melt completely；
2) polyacid component p-phthalic acid 50-70wt% is added,
M-phthalic acid 0-10wt%
Adipic acid 0-10wt%
Being warmed up to 240-260 DEG C carries out esterification；Until system acid number is less than 15mgKOH/g；
3) 220-230 DEG C is cooled to, progressively evacuation polycondensation, vacuum is 40-50mbar, reacts 1-3 hours, acid number is little
In 10mgKOH/g, hydroxyl value is in 40-50mgKOH/g；
4) 150-160 DEG C is cooled to, acidolysis agent trimellitic anhydride 0-10wt% is added, 2-5 hours are reacted, and adjusts body
It is acid number to 25-35mgKOH/g, hydroxyl value to 25-35mgKOH/g；
5) after reaction terminates, antioxidant H (0-0.1wt%) and curing accelerator (0-0.5wt%) are added, stirs 20-30
Resin can discharge after minute is uniform, and cooling crush is standby；Relative to the gross weight for all feeding intake.
Hydroxycarboxyl group difunctional polyester resin refers to the polyester resin of synthesis both containing the hydroxy functional group that hydroxyl value is higher,
Again containing the higher carboxyl functional group of acid number.
The present invention compared with prior art, has used different starting monomers and catalyst system, has synthesized new hydroxyl
With carboxyl difunctional polyester resin, can obtain the powdery paints of higher levelling and mechanical performance is used for the fields such as thermal transfer.
The powdery paints obtained using hydroxycarboxyl group difunctional polyester, with same acid number simple function group polyester, same hydroxyl
Powdery paints prepared by the powdery paints and both polyester physical mixed that value simple function group polyester resin does compares, and has
Preferably levelling, is easier paper-tear picture after gloss and thermal transfer.
Method of testing
Number-average molecular weight is tested with GPC (gel permeation chromatography).
Melt viscosity is to use Brookfield viscometers, resin is placed on and is heated on 160 DEG C of viscometer, when resin
Melt completely, test its viscosity.
Fusing point test adopts DSC differential scanning calorimetries, resin melting to absorb heat, and can obtain melting by DSC bent
Line, calculate and baseline area can with obtain its melting point values.
Degree of crystallinity is tested：DSC differential scanning calorimetries.When crystalline polymer is melted all can heat release, it is molten that DSC determines its crystallization
When melting, the area that the melting peak curve for obtaining and baseline are surrounded can directly be converted into heat, and this heat is in crystalline polymer
The melting heat of crystalline portion, the melting heat of polymer is directly proportional to degree of crystallinity, and degree of crystallinity is higher, and melting heat is bigger.If it is known that
Melting heat (can check in from document) when road polymer is very crystallized, then degree of crystallinity=(melt Resin crystallization part
Melt heat)/very crystalline fusion heat.
1. method of testing
2. raw material and the supplier of polyester and production powdery paints are produced
Embodiment 1：
By 463.9 grams of neopentyl glycols, 0.5 gram of tributyltin oxide and 0.85 gram of trinonylphengl phosphite addition nitrogen ring
In the reactor that lower 6 liters of border, intensification be heated to 150 DEG C or so, the neopentyl glycol monomer in observing response device melt completely after again
34.9 g of adipic acid and 592.8 grams of terephthalic acid monomers are added, is stirred.250 DEG C are heated to, in this reaction condition
Under, there is esterifying polycondensation reaction in dihydroxylic alcohols and dicarboxylic acid monomer, be incubated to the acid number of reaction system and be less than 15mgKOH/g.Stop
Heating, controls the temperature of reaction system to 220 DEG C, then vacuum polycondensation, and vacuum is 40-50mbar, 1-2 hours.Sampling point
Analysis acid number and hydroxyl value, acid number should be less than 10mgKOH/g, and hydroxyl value should be in 46-50mgKOH/g.Stop heating, by reaction system
Temperature be down to 160 DEG C from 220 DEG C, be subsequently adding 63 grams of trimellitic anhydrides, there is acidifying open loop with anhydride in terminal hydroxy group resin
Reaction.3 hours, sample analysis acid number and hydroxyl value are reacted at this temperature.When acid number is that 30mgKOH/g, hydroxyl value are
During 35mgKOH/g, 1 gram of 2,6- di-tert-butyl-4-methy phenol is added, resin discharging after mixing 30 minutes obtains resin 1.
Embodiment 2：
Raw material composition is identical with embodiment 1 with synthesis technique, obtains resin 2.In order to study the heat stability of resin, work as tree
In set point, resin carries out the heat stability testing of 8 hours to the acid number and hydroxyl value of fat under conditions of 160 DEG C.
Embodiment 3：
By 415 grams of neopentyl glycols, 52 grams of trimethylolpropanes, 0.5 gram of tributyltin oxide and 0.85 gram of trinonylphengl Asia
Phosphate ester is added in the reactor of lower 6 liters of nitrogen environment, and intensification is heated to 150 DEG C or so, and the alcohol monomer in observing response device is complete
677 grams of terephthalic acid monomers are added after full-fusing, is stirred.It is heated to 250 DEG C, at this point in the reaction, two
There is esterified polycondensation reaction in first alcohol and dicarboxylic acid monomer, be incubated to the acid number of reaction system and be less than 15mgKOH/g.Stop heating,
To 230 DEG C, at this temperature, vacuum polycondensation is less than 8mgKOH/g, hydroxyl to the temperature of control reaction system until the acid number of resin
Value is in 55-65mgKOH/.1 gram of 2,6- di-tert-butyl-4-methy phenol is added, resin discharging after mixing 30 minutes obtains resin
3。
Embodiment 4：
By 349.4 grams of neopentyl glycols, 28 grams of ethylene glycol, 24.2 grams of trimethylolpropanes, 0.5 gram of tributyltin oxide and
0.85 gram of trinonylphengl phosphite is added in the reactor of lower 6 liters of nitrogen environment, and intensification is heated to 150 DEG C or so, and observation is anti-
Answer the alcohol monomer in device that 636.5 grams of terephthalic acid monomers are added after melting completely, stir.250 DEG C are heated to,
At this point in the reaction, there is esterified polycondensation reaction in dihydroxylic alcohols and dicarboxylic acid monomer, is incubated to the acid number of reaction system and is less than
15mgKOH/g.Stop heating, control the temperature of reaction system to 205 DEG C, at this temperature, 59.3 g of adipic acid and 43.3 grams
Trimellitic anhydride adds reaction system.When reaction system tip temperature be less than 80 DEG C when, sampling detection resin acid number and
Hydroxyl value, in the state of resin clarification, acid number should be less than 65mgKOH/g.At this temperature vacuum polycondensation is until the acid of resin
Value is less than 5mgKOH/g in 55-65mgKOH/g, hydroxyl value.1 gram of 2,6- di-tert-butyl-4-methy phenol is added, is mixed 30 minutes
Afterwards resin can discharge, and obtain resin 4.
2. powder coating component proportioning and its spreading property
The preparation of powdery paints：1. by all raw material polyester, cross-linking agent, catalyst, streams for manufacturing powdery paints
The premixing in premixing machine of flat agent, pigment and defoamer；2. by through the raw material of premixing through extruder melting extrusion；3. will
The material cooling tabletting of melting extrusion；4. tablet is crushed by pulverizer and sieved, obtain the powder particle of appropriate particle size
As powdery paints.
Comparative example：
Claims (6)
1. a kind of thermal transfer hydroxycarboxyl group difunctional polyester resin used for powder coating, the acid number with 25-35mgKOH/g and
The hydroxyl value of 25-35mgKOH/g, degree of crystallinity 0-85%, fusing point is 120-180 DEG C, and 160 DEG C of melt viscosity is 10-100Pa.s,
Number-average molecular weight is 3000-5000, it is characterised in that obtained by the raw material Jing melt polycondensation reactions of following percentage by weight：
Polyol component neopentyl glycol 30-50wt%
Ethylene glycol 0-10wt%
Trimethylolpropane 0-10wt%
Polyacid component p-phthalic acid 50-70wt%,
M-phthalic acid 0-10wt%
Adipic acid 0-10%
Acidolysis agent trimellitic anhydride 0-10wt%
Esterification catalyst 0-0.1wt%.
2. polyester resin as claimed in claim 1, is prepared by following methods,
1) polyol component neopentyl glycol 30-50wt% is added
Ethylene glycol 0-10wt%
Trimethylolpropane 0-10wt%
With esterification catalyst component 0-0.1wt% adds antioxidant G (0-0.1wt%) to be gradually heating to 140- while stirring
160 DEG C make it melt completely；
2) polyacid component p-phthalic acid 50-70wt% is added,
M-phthalic acid 0-10wt%
Adipic acid 0-10wt%
Being warmed up to 240-260 DEG C carries out esterification；Until system acid number is less than 15mgKOH/g；
3) 220-230 DEG C is cooled to, progressively evacuation polycondensation, vacuum is 40-50mbar, reacts 1-3 hours, acid number is less than
10mgKOH/g, hydroxyl value is in 40-50mgKOH/g；
4) 150-160 DEG C is cooled to, acidolysis agent trimellitic anhydride 0-10wt% is added, 2-5 hours, and regulation system acid is reacted
It is worth to 25-35mgKOH/g, hydroxyl value to 25-35mgKOH/g；
5) after reaction terminates, antioxidant H (0-0.1wt%) and curing accelerator (0-0.5wt%) are added, stirs 20-30 minutes
Resin can discharge after uniform, and cooling crush is standby；Relative to the gross weight for all feeding intake.
3. polyester resin as claimed in claim 1, it is characterised in that described esterification catalyst is tin catalyst, selected from two
Butyl stannum oxide, tributyltin oxide, dihydroxy dibutyl tin oxide, one or several in stannous oxalate.
4. polyester resin as claimed in claim 1, it is characterised in that described curing accelerator can be selected from tetraethyl bromination
Ammonium, 4 bromide, benzyltriethylammoinium chloride, one or more in triphenyl ethyl phosphonium bromide phosphorus.
5. polyester resin as claimed in claim 1, it is characterised in that described antioxidant G and antioxidant H can be identical
Or different antioxidant, the antioxidant is selected from Hinered phenols primary antioxidant and/or phosphorous acid esters auxiliary antioxidant.
6. it is a kind of to prepare the method that thermal transfer hydroxycarboxyl group dual intensity used for powder coating rolls into a ball polyester resin, comprise the steps of：
1) polyol component neopentyl glycol 30-50wt% is added
Ethylene glycol 0-10wt%
Trimethylolpropane 0-10wt%
With esterification catalyst component 0-0.1wt% adds antioxidant G (0-0.1wt%), and 140- is gradually warmed up to while stirring
160 DEG C melt completely to it；
2) polyacid component p-phthalic acid 50-70wt% is added,
M-phthalic acid 0-10wt%
Adipic acid 0-10wt%
Being warmed up to 240-260 DEG C carries out esterification；Until system acid number is less than 15mgKOH/g；
3) 220-230 DEG C is cooled to, progressively evacuation polycondensation, vacuum is 40-50mbar, 1-3 hours, acid number is less than
10mgKOH/g, hydroxyl value is about in 40-50mgKOH/g；
4) 150-160 DEG C is cooled to, acidolysis agent trimellitic anhydride 0-10wt%, reaction 3-5 hours, and regulation system is added
Acid number is to 25-35mgKOH/g, hydroxyl value to 25-35mgKOH/g；When acid number and hydroxyl value reach this scope, as terminal can be with
Cooling；
5) after reaction terminates, the additives such as antioxidant H (0-0.1wt%) and curing accelerator (0-0.5wt%), stirring are added
Resin can discharge after 20-30 minute mix homogeneously, and cooling is broken standby；Relative to the gross weight for all feeding intake.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107868235A (en) * | 2017-10-30 | 2018-04-03 | 广州擎天材料科技有限公司 | A kind of powdery paints difunctional polyester resin and preparation method thereof |
| CN107936788A (en) * | 2017-11-13 | 2018-04-20 | 广州擎天材料科技有限公司 | Powder coating for thermal transfer printing |
| CN107964093A (en) * | 2017-09-29 | 2018-04-27 | 广东依斯特新材料有限公司 | Powdery paints hydroxyl telechelic polyester resin, preparation method and obtained powdery paints |
| CN110527412A (en) * | 2019-10-22 | 2019-12-03 | 广西南宁维一防腐科技有限公司 | Environment-friendly curing thermal transfer printing powder and preparation method thereof |
| CN110982410A (en) * | 2019-12-19 | 2020-04-10 | 长沙金久锌钢型材有限公司 | Electrostatic spraying powder coating and preparation method and application thereof |
| CN111087587A (en) * | 2018-10-24 | 2020-05-01 | 帝兴树脂(昆山)有限公司 | Bifunctional polyester resin for super-weather-resistant heat transfer printing powder coating and preparation method thereof |
| CN115124701A (en) * | 2022-08-10 | 2022-09-30 | 浙江超浪新材料有限公司 | Bifunctional polyester resin, powder coating and application |
| CN117264510A (en) * | 2023-10-07 | 2023-12-22 | 安徽智成实业有限公司 | Polyester resin for thick coating pinhole-resistant self-curing powder coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107964093A (en) * | 2017-09-29 | 2018-04-27 | 广东依斯特新材料有限公司 | Powdery paints hydroxyl telechelic polyester resin, preparation method and obtained powdery paints |
| CN107868235A (en) * | 2017-10-30 | 2018-04-03 | 广州擎天材料科技有限公司 | A kind of powdery paints difunctional polyester resin and preparation method thereof |
| CN107936788A (en) * | 2017-11-13 | 2018-04-20 | 广州擎天材料科技有限公司 | Powder coating for thermal transfer printing |
| CN111087587A (en) * | 2018-10-24 | 2020-05-01 | 帝兴树脂(昆山)有限公司 | Bifunctional polyester resin for super-weather-resistant heat transfer printing powder coating and preparation method thereof |
| CN110527412A (en) * | 2019-10-22 | 2019-12-03 | 广西南宁维一防腐科技有限公司 | Environment-friendly curing thermal transfer printing powder and preparation method thereof |
| CN110982410A (en) * | 2019-12-19 | 2020-04-10 | 长沙金久锌钢型材有限公司 | Electrostatic spraying powder coating and preparation method and application thereof |
| CN115124701A (en) * | 2022-08-10 | 2022-09-30 | 浙江超浪新材料有限公司 | Bifunctional polyester resin, powder coating and application |
| CN115124701B (en) * | 2022-08-10 | 2023-12-22 | 浙江超浪新材料有限公司 | Difunctional polyester resin, powder coating and application |
| CN117264510A (en) * | 2023-10-07 | 2023-12-22 | 安徽智成实业有限公司 | Polyester resin for thick coating pinhole-resistant self-curing powder coating and preparation method thereof |
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