CN107177314B - Method for preparing rosin diene addition product polyol ester resin from rosin - Google Patents
Method for preparing rosin diene addition product polyol ester resin from rosin Download PDFInfo
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- CN107177314B CN107177314B CN201710492276.XA CN201710492276A CN107177314B CN 107177314 B CN107177314 B CN 107177314B CN 201710492276 A CN201710492276 A CN 201710492276A CN 107177314 B CN107177314 B CN 107177314B
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- rosin
- diene
- ester resin
- polyol ester
- reaction
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 90
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 89
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 239000011347 resin Substances 0.000 title claims abstract description 39
- -1 polyol ester Chemical class 0.000 title claims abstract description 38
- 229920005862 polyol Polymers 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- 150000001993 dienes Chemical class 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 150000003077 polyols Chemical class 0.000 claims abstract description 4
- 230000032050 esterification Effects 0.000 claims abstract description 3
- 238000005886 esterification reaction Methods 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 100
- 239000000178 monomer Substances 0.000 claims description 14
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000009835 boiling Methods 0.000 abstract description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 abstract 1
- 239000000600 sorbitol Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The method for preparing the rosin diene addition product polyol ester resin from rosin comprises the following steps: (1) adding rosin into a reaction kettle, heating to 150-; (2) raising the temperature to 195-220 ℃, adding a metal oxide catalyst, dropwise adding a polyol and a sorbitol modifier for esterification, controlling the temperature to be 220-270 ℃, and reacting for 5-10 hours; (3) vacuum decompressing to distill out low boiling point fraction, and the resin in the kettle is rosin diene addition product polyol ester resin. The method for preparing the rosin diene addition product polyol ester resin from the rosin has the advantages of simple process flow, environmental protection and renewable raw materials, can be used for preparing pure water environment-friendly tackifying emulsion, is used in pressure sensitive adhesive emulsion such as acrylic emulsion and has better compatibility with the acrylic emulsion.
Description
Technical field
The present invention relates to a kind of method that rosin Diene-addition thing polyol ester resin is prepared from rosin.
Background technology
Rosin is a kind of di-terpene resin acid of solid, its molecule contains tricyclic phenanthrene skeleton structure, a carboxyl, and one altogether
Yoke double bond.Using the carboxyl in rosin and double bond can be esterified and addition reaction, and the rosin tree of different physicochemical properties is made
Fat.
It is existing as follows with the technology retrieval for preparing rosin deep processing resinoid：
Chinese patent CN201010578625.8, a kind of manufacture method of colourless hydrogenated rosin ester resin.One kind is invented
The manufacture method of colourless hydrogenated rosin ester resin, using the rosin by distilation, again through being esterified obtained rosin ester as raw material,
The catalytic hydrogenation under the action of solvent and effective catalyst, then through separated solvent, obtains colourless hydrogenated rosin ester resin.
Chinese patent CN 201210149937.6, a kind of Low-temperature resistant rosin tackifying resin, preparation method and the usage.Should
A kind of preparation method of Low-temperature resistant rosin tackifying resin of disclosure of the invention, the described method comprises the following steps：In inert gas shielding
Under, after rosin is melted, with polyol reaction under catalyst action, when reaction 4-24 is small at 200-290 DEG C, discharging, obtains
Polyalcohol modified rosin ester, then under inert gas shielding, the polyalcohol modified rosin ester and higher fatty acids are existed
Reacted at 200-290 DEG C, reaction 4-24 it is small when after discharge, obtain rosin tackifying resin.
In conclusion research and application of the people to rosin are done a lot of work, but have not seen related acrylic acid series
List body and D-sorbite modifier are modified the research report of rosin.
The content of the invention
The present invention seeks to be to provide a kind of method for preparing rosin Diene-addition thing polyol ester resin from rosin.
To achieve these goals, the present invention is achieved by the following technical solutions：
A kind of method that rosin Diene-addition thing polyol ester resin is prepared from rosin, it is characterised in that according to the following steps
Carry out：
(1) rosin is added in reaction kettle, is warming up to 150-195 DEG C, close Diene-addition agent and monomer I is successively added, stirs
Heating reflux reaction is mixed, the monomer I includes oleic series monomer；
(2) 195-220 DEG C is raised the temperature to, adds metal oxide catalyst, polyalcohol is added dropwise and D-sorbite changes
Property thing carry out esterification, control temperature at 220~270 DEG C, reaction 5-10 it is small when；
(3) vacuum decompression steams low boiler cut, and the resin in kettle is rosin Diene-addition thing polyol ester resin.
Further, after close Diene-addition agent progress addition reaction is first added dropwise in the step (1), then monomer I is added dropwise, stirs
Mix, 150-195 DEG C of controlling reaction temperature, when clock reaction 1-6 is small after reflux occurs in reaction.
Further, after polyol reaction being added dropwise in the step (2), D-sorbite modifier is added.
Further, the step (3), which first samples, surveys acid value, and acid value reaches vacuum decompression steaming again after 140-190mgKOH/g
Evaporate, control and steam low boiler cut at 220-270 DEG C.
Further, the close Diene-addition agent is the one or more of maleic anhydride, maleic acid, fumaric acid, close diene
Addition agent dosage and the weight ratio of rosin dosage are (2.00~8.00)：100.
Further, the oleic series monomer in step (1) be acrylic acid, methacrylic acid, ethyl methacrylate,
One or more in Isooctyl acrylate monomer, butyl methacrylate, butyl acrylate, the weight of monomer I dosages and rosin dosage
It is (6.00~13.00) to measure ratio：100.
Further, monomer I further includes one or both of styrene, isoprene described in step (1).Benzene second
The addition of alkene, isoprene can make the product of the present invention preferably hold viscosity.
Further, the metal oxide catalyst is the one or more of zinc oxide, magnesia, calcium oxide, metal
Oxide catalyst dosage is the 0.1%~2.0% of rosin weight.
Further, the metal oxide catalyst is the one or more of zinc oxide, magnesia, calcium oxide.
Further, the polyalcohol is the one or more of glycerine, pentaerythrite, ethylene glycol, diethylene glycol (DEG), triethylene glycol,
Polyalcohol dosage and the weight ratio of rosin dosage are (1.00~8.00)：100.
Further, the D-sorbite modifier is double (to methyl benzylidene) D-sorbite, double (dimethyl Asia benzene
Base) D-sorbite, one kind or its mixture of double (benzylidene) D-sorbites, D-sorbite modifier dosage and rosin dosage
Weight ratio be (1.00~6.00)：100.
The method that the slave rosin of the present invention prepares rosin Diene-addition thing polyol ester resin, has the advantages that：
(1) method that the present invention prepares rosin Diene-addition thing polyol ester resin from rosin, technological process is simple, and ring
Border is friendly, raw material is renewable resource；
(2) rosin Diene-addition thing polyol ester resin prepared by the present invention, as a kind of high softening-point modified rosin tree
Fat, available for preparing water-based environmental protection Tackified emulsion, in the pressure-sensitive adhesive emulsions such as acrylic emulsion, with acrylic emulsion have compared with
Good compatibility, can effectively improve its tack and peel strength, and keep it to hold viscosity.
Embodiment
Embodiment 1
The method that the slave rosin of the present embodiment prepares rosin Diene-addition thing polyol ester resin, carries out according to the following steps：
(1) raw material of following parts by weight is weighed by table 1, have the function of stirring, reflux, distilling apparatus 500ml four
In mouthful flask, rosin is added, is warming up to 150-160 DEG C, then plus fumaric acid, agitating and heating back flow reaction, after reaction 30 minutes,
Acrylic acid, stirring, 185-195 DEG C of controlling reaction temperature, when clock reaction 2 is small after reflux occurs in reaction is added dropwise；
Table 1
| Raw material | Parts by weight |
| Rosin | 100 |
| Fumaric acid | 8 |
| Acrylic acid | 13 |
| Zinc oxide | 0.1 |
| Diethylene glycol (DEG) | 5 |
| Double (dimethylphenylene) D-sorbites | 6 |
(2) reaction temperature is brought up to 195~220 DEG C, adds zinc oxide, reacted 20 minutes, diethylene glycol (DEG), reaction 30 is added dropwise
After minute, double (dimethylphenylene) D-sorbites are added, reaction temperature brings up to 220~240 DEG C, when reaction 10 is small；
(3) acid value is surveyed in sampling, and vacuum (20mmHg) depressurizes after acid value reaches 140-190mgKOH/g, and material temperature is controlled in 220-
Low-boiling component is steamed at 240 DEG C, resin is rosin Diene-addition thing polyester resin in bottle.
Embodiment 2
The method that the slave rosin of the present embodiment prepares rosin Diene-addition thing polyol ester resin, carries out according to the following steps：
(1) raw material of following parts by weight is weighed by table 2, have the function of stirring, reflux, distilling apparatus 500ml four
In mouth flask, rosin being added, is warming up to 150-160 DEG C, then add maleic acid, agitating and heating back flow reaction, reacts after ten minutes,
Methacrylic acid, stirring, 150-170 DEG C of controlling reaction temperature, when clock reaction 4 is small after reflux occurs in reaction is added dropwise；
Table 2
| Raw material | Parts by weight |
| Rosin | 100 |
| Maleic acid | 3 |
| Methacrylic acid | 10 |
| Magnesia | 0.13 |
| Glycerine | 3 |
| Double (benzylidene) D-sorbites | 3 |
(2) reaction temperature is brought up to 210~220 DEG C, adds magnesia, reacted 40 minutes, glycerine is added dropwise, react 60 points
Zhong Hou, adds double (benzylidene) D-sorbites, and reaction temperature brings up to 250-270 DEG C, when reaction 6 is small；
(3) acid value is surveyed in sampling, and vacuum (20mmHg) depressurizes after acid value reaches 140-190mgKOH/g, and material temperature is controlled in 240-
Low-boiling component is steamed at 250 DEG C, resin is rosin Diene-addition thing polyester resin in bottle.
Embodiment 3
The method that the slave rosin of the present embodiment prepares rosin Diene-addition thing polyol ester resin, carries out according to the following steps：
(1) raw material of following parts by weight is weighed by table 3, have the function of stirring, reflux, distilling apparatus 500ml four
In mouth flask, rosin is added, is warming up to 170-180 DEG C, then add maleic anhydride, agitating and heating back flow reaction, reacts 40 minutes
Afterwards, butyl acrylate and styrene, stirring, 170-180 DEG C of controlling reaction temperature, clock reaction after reaction flows back is added dropwise
6 it is small when；
Table 3
| Raw material | Parts by weight |
| Rosin | 100 |
| Maleic anhydride | 2 |
| Styrene | 8 |
| Butyl acrylate | 3 |
| Calcium oxide | 1 |
| Triethylene glycol | 8 |
| Double (to methyl benzylidene) D-sorbites | 1 |
(2) reaction temperature is brought up to 200-210 DEG C, adds calcium oxide, reacted 20 minutes, triethylene glycol, reaction 60 is added dropwise
After minute, double (to methyl benzylidene) D-sorbites are added, reaction temperature brings up to 240-250 DEG C, when reaction 8 is small；
(3) acid value is surveyed in sampling, and vacuum (20mmHg) depressurizes after acid value reaches 140-190mgKOH/g, and material temperature is controlled in 250-
Low-boiling component is steamed at 270 DEG C, resin is rosin Diene-addition thing polyester resin in bottle.
Embodiment 4
The method that the slave rosin of the present embodiment prepares rosin Diene-addition thing polyol ester resin, carries out according to the following steps：
(1) raw material of following parts by weight is weighed by table 4, have the function of stirring, reflux, distilling apparatus 500ml four
In mouthful flask, rosin is added, is warming up to 180-195 DEG C, then plus fumaric acid, agitating and heating back flow reaction, after reaction 90 minutes,
Isooctyl acrylate monomer and isoprene is added dropwise, stirring, 180-195 DEG C of controlling reaction temperature, timing is anti-after reaction flows back
Answer 1 it is small when；
Table 4
(2) reaction temperature is brought up to 210-220 DEG C, adds zinc oxide, reacted 20 minutes, pentaerythrite, reaction is added dropwise
After 50 minutes, double (to methyl benzylidene) D-sorbites are added, reaction temperature brings up to 260-270 DEG C, when reaction 5 is small；
(3) acid value is surveyed in sampling, and vacuum (20mmHg) depressurizes after acid value reaches 140-190mgKOH/g, and material temperature is controlled in 260-
Low-boiling component is steamed at 270 DEG C, resin is rosin Diene-addition thing polyester resin in bottle.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Cannot therefore it be construed as limiting the scope of the patent.It should be pointed out that come for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.
Claims (9)
- A kind of 1. method that rosin Diene-addition thing polyol ester resin is prepared from rosin, it is characterised in that according to the following steps into OK：(1) rosin is added in reaction kettle, is warming up to 150-195 DEG C, successively adds close Diene-addition agent and monomer I, stirring adds Hot back flow reaction, the monomer I include oleic series monomer；(2) 195-220 DEG C is raised the temperature to, adds metal oxide catalyst, polyalcohol and D-sorbite modifier is added dropwise Esterification is carried out, the D-sorbite modifier is double (to methyl benzylidene) D-sorbite, double (dimethylphenylene) The one or more of D-sorbite, double (benzylidene) D-sorbites, control 220~270 DEG C of temperature, when reaction 5-10 is small；(3) acid value is surveyed in first sampling, and acid value reaches vacuum decompression distillation again after 140-190mgKOH/g, controls at 220-270 DEG C Steam low boiler cut, the resin in kettle is rosin Diene-addition thing polyol ester resin.
- 2. the method according to claim 1 that rosin Diene-addition thing polyol ester resin is prepared from rosin, its feature exist In, close Diene-addition agent is first added dropwise in the step (1) and carries out addition reaction, then monomer I is added dropwise, stir, controlling reaction temperature 150-195 DEG C, when clock reaction 1~6 is small after reflux occurs in reaction.
- 3. the method according to claim 1 that rosin Diene-addition thing polyol ester resin is prepared from rosin, its feature exist After polyol reaction is added dropwise in, the step (2), D-sorbite modifier is added.
- 4. a kind of method that rosin Diene-addition thing polyol ester resin is prepared from rosin according to claim 1, it is special Sign is, parent's Diene-addition agent is the one or more of maleic anhydride, maleic acid, fumaric acid, close Diene-addition agent dosage Weight ratio with rosin dosage is (2.00~8.00)：100.
- 5. the method according to claim 1 that rosin Diene-addition thing polyol ester resin is prepared from rosin, its feature exist It is that acrylic acid, methacrylic acid, ethyl methacrylate, acrylic acid are different pungent in, oleic series monomer described in step (1) One or more in ester, butyl methacrylate, butyl acrylate, the weight ratio of the monomer I dosages and rosin dosage are (6.00~13.00)：100.
- 6. the method according to claim 1 that rosin Diene-addition thing polyol ester resin is prepared from rosin, its feature exist In monomer I further includes one or both of styrene, isoprene described in step (1).
- 7. the method according to claim 1 that rosin Diene-addition thing polyol ester resin is prepared from rosin, its feature exist In the metal oxide catalyst is the one or more of zinc oxide, magnesia, calcium oxide, and metal oxide catalyst is used Amount is the 0.1%~2.0% of rosin weight.
- 8. the method according to claim 1 that rosin Diene-addition thing polyol ester resin is prepared from rosin, its feature exist In the polyalcohol is the one or more of glycerine, pentaerythrite, ethylene glycol, diethylene glycol (DEG), triethylene glycol, polyalcohol dosage and pine The weight ratio of fragrant dosage is (1.00~8.00)：100.
- 9. the method according to claim 1 that rosin Diene-addition thing polyol ester resin is prepared from rosin, its feature exist In D-sorbite modifier dosage and the weight ratio of rosin dosage are (1.00~6.00)：100.
Priority Applications (1)
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