CN106496480A - One-step method environmental protection type resin and its preparation technology - Google Patents
One-step method environmental protection type resin and its preparation technology Download PDFInfo
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- CN106496480A CN106496480A CN201510563314.7A CN201510563314A CN106496480A CN 106496480 A CN106496480 A CN 106496480A CN 201510563314 A CN201510563314 A CN 201510563314A CN 106496480 A CN106496480 A CN 106496480A
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Abstract
The invention belongs to printing-ink manufacturing industry resin art, more particularly to one-step method environmental protection type resin and its preparation technology, characterized in that, including Colophonium, Oleum Verniciae fordii, Cardanol, paraformaldehyde, glycerol, tetramethylolmethane, cis-butenedioic anhydride, magnesium oxide, each component is consisted of by mass fraction：Colophonium 55-60 parts, Oleum Verniciae fordii 5-10 parts, Cardanol 15-25 parts, paraformaldehyde 5-10 parts, glycerol 2-5 parts, tetramethylolmethane 2-3 parts, cis-butenedioic anhydride 0.5-1 parts, catalyst 0.1-0.5 parts, in the Colophonium of melting, Cardanol and paraformaldehyde are condensed in the presence of catalyst, additive reaction is carried out with Colophonium, increase resin structure using cis-butenedioic anhydride, then glycerol is used, tetramethylolmethane carries out esterification evacuation and obtains naval stores, the present invention adopts one-step method, compare traditional two-step method, phenolic resin need not be washed, a large amount of formaldehyde-containing wastewaters are not produced, reduce environmental pollution, saving water resource, production cost is saved.
Description
Technical field
The invention belongs to printing-ink manufacturing industry resin art, more particularly to one-step method environmental protection type resin and its preparation technology.
Background technology
With establishing and improve for environmental regulation, Chinese printing industry is being developed towards environment-friendly products direction, and enterprise is changed into by past passive requirement and is actively changed, and the social responsibility of environmental protection is greatly strengthened.Market increasingly will increase to the demand of environmental protection and sustainable ink.As the innovative product with environmental protection and economical effects emerges in an endless stream, the market of solvent-borne type and petroleum base ink is also gradually being replaced by the environment-friendly products that recent development goes out.At present, traditional resin in ink is produced using two-step method, in process of production, needs to wash phenolic resin, produces a large amount of formaldehyde-containing wastewaters, and waste water resource pollutes environment.
Content of the invention
For solving above-mentioned technical problem, the invention provides a kind of one-step method environmental protection type resin and its preparation technology without the need for washing.
The technical solution adopted in the present invention is：
One-step method environmental protection type resin, it is characterised in that including Colophonium, Oleum Verniciae fordii, Cardanol, paraformaldehyde, glycerol, tetramethylolmethane, cis-butenedioic anhydride, magnesium oxide, each component is consisted of by mass fraction：Colophonium 55-60 parts, Oleum Verniciae fordii 5-10 parts, Cardanol 15-25 parts, paraformaldehyde 5-10 parts, glycerol 2-5 parts, tetramethylolmethane 2-3 parts, cis-butenedioic anhydride 0.5-1 parts, catalyst 0.1-0.5 parts.
Each component is consisted of by more high quality number：60 parts of Colophonium, 7 parts of Oleum Verniciae fordii, 22 parts of Cardanol, 8 parts of paraformaldehyde, 3 parts of glycerol, 2.5 parts of tetramethylolmethane, 0.6 part of cis-butenedioic anhydride, 0.1 part of catalyst.
The Cardanol adopts pure natural plant extract, and the degree of polymerization of the paraformaldehyde is 8-12.
The catalyst is magnesium oxide.
The amount of the magnesium oxide accounts for the 0.2-1.5% of Colophonium consumption.
The Cardanol is 1 with the ratio of the amount of the material of paraformaldehyde：1.6～1：2.5.
The preparation technology of one-step method environmental protection type resin, it is characterised in that comprise the following steps：
（1）Colophonium, Oleum Verniciae fordii are heated to melting, in the Colophonium for melting, add Cardanol and paraformaldehyde, add catalyst control temperature to make phenol formaldehyde condensation, then additive reaction is carried out with Colophonium；
（2）To the step（1）Product in add cis-butenedioic anhydride to carry out D-A reactions, increase the space structure of resin；
（3）To the step（2）Product in add glycerol, tetramethylolmethane to carry out esterification, reaction controlling at 255 DEG C -265 DEG C, after reaction 4 hours, vacuum distillation, you can.
The step（1）In, Cardanol is 110 DEG C -116 DEG C with the more excellent condensation temp of paraformaldehyde, Cardanol：The amount ratio of the more excellent material of Colophonium is 0.3：1～0.8：1.
The step（3）In, glycerol is 0.5 with the amount ratio of the more excellent material of tetramethylolmethane：1～3：1, the more excellent time 4-6 hours of esterification.
The step（3）In, gained resin viscosity >=6000mpa.s/25 DEG C, acid number≤25mgKOH/g, normal heptane value >=5 ml/2g are as qualified.
Beneficial effects of the present invention are：
1st, the present invention is by the Colophonium of melting, Cardanol and paraformaldehyde are condensed in the presence of catalyst, additive reaction is carried out with Colophonium, increases resin structure using cis-butenedioic anhydride, esterification evacuation is then carried out with glycerol, tetramethylolmethane and obtains naval stores, the present invention adopts one-step method, compare traditional two-step method, it is not necessary to which phenolic resin is washed, do not produce a large amount of formaldehyde-containing wastewaters, environmental pollution, saving water resource is not only reduced, production cost is also a saving；
2nd, the Cardanol used by the production of resins in the present invention is pure natural plant extract matter, pollution-free, replace the environmental protection organizations such as traditional bisphenol-A, Cardanol, nonyl phenol disabling phenols, the product for preparing has the advantages that softening point height, good viscoelasticity, lighter color, dissolubility are good, for being suitable for the resin that environment-friendly ink is used, the ink product that produces has good printability and transferability, printing is bright in luster, abundant and beautiful, there is preferable gloss and refreshing dryness, may be adapted to the colored printing of wide scope；
3rd, resin not only environmental protection prepared by the present invention, and the high viscosity have the advantages that conventional resins, molecular weight be big, set is fast.
Specific embodiment
One-step method environmental protection type resin, including Colophonium, Oleum Verniciae fordii, Cardanol, paraformaldehyde, glycerol, tetramethylolmethane, cis-butenedioic anhydride, magnesium oxide, each component is consisted of by mass fraction：Colophonium 55-60 parts, Oleum Verniciae fordii 5-10 parts, Cardanol 15-25 parts, paraformaldehyde 5-10 parts, glycerol 2-5 parts, tetramethylolmethane 2-3 parts, cis-butenedioic anhydride 0.5-1 parts, catalyst 0.1-0.5 parts.
Each component is consisted of by more high quality number：60 parts of Colophonium, 7 parts of Oleum Verniciae fordii, 22 parts of Cardanol, 8 parts of paraformaldehyde, 3 parts of glycerol, 2.5 parts of tetramethylolmethane, 0.6 part of cis-butenedioic anhydride, 0.1 part of catalyst.
Wherein, Cardanol adopts pure natural plant extract, and the degree of polymerization of paraformaldehyde is 8-12, and catalyst is magnesium oxide, and the consumption of magnesium oxide is the 0.2-1.5% of Colophonium consumption, and Cardanol is 1 with the ratio of the amount of the material of paraformaldehyde：1.6～1：2.5.
One-step method environmental protection type resin is preparation technology, comprises the following steps：（1）Colophonium, Oleum Verniciae fordii are heated to melting, in the Colophonium for melting, add Cardanol and paraformaldehyde, add catalyst control temperature to make phenol formaldehyde condensation, then additive reaction is carried out with Colophonium；（2）To step（1）Product in add cis-butenedioic anhydride to carry out D-A reactions, increase the space structure of resin；（3）To step（2）Product in add glycerol, tetramethylolmethane to carry out esterification, reaction controlling at 255 DEG C -265 DEG C, after reaction 4 hours, vacuum distillation.
Wherein, step（1）In, Cardanol is 110-116 DEG C with the more excellent condensation temp of paraformaldehyde, Cardanol：The amount ratio of the more excellent material of Colophonium is 0.3：1～0.8：1；Step（3）In, glycerol is 0.5 with the amount ratio of the more excellent material of tetramethylolmethane：1～3：1, the more excellent time 4-6 hours of esterification；Step（3）In, gained resin viscosity >=6000mpa.s/25 DEG C, acid value≤25mgKOH/g, normal heptane value >=5 ml/2g are as qualified.
The temperature height is condensed with paraformaldehyde by Cardanol is for the property indices of product also have a great impact, in order that reactivity reaches most preferably, suitable condensation temp must be selected, if condensation temp is too low, the reactivity of alkylphenol is low, in condensation substance, active methylol content is low, and final products viscosity is low, does not reach use requirement；Condensation temp is too high, then acutely, in condensation substance, trimer and tetrameric ratio increase, and active methylol content reduces, and final products viscosity can also reduce for alkylphenol reaction, and condensation temp selects to be advisable between 110-116 DEG C.
Under identical enzymatic synthesis condition, the ratio of Cardanol and Colophonium consumption also has considerable influence to properties of product, and Cardanol consumption is little, and the viscosity of product is low, and the printing-ink body bone that makes is poor, and printing on-line shop is unintelligible；Cardanol consumption is big, and the viscosity of product is high, and acid number is not easy to lower, implode phenomenon easily occurs, and product oil-soluble is poor, gel degree height, and the viscosity of printing ink that makes, viscosity are excessive, it is impossible to use, and the amount ratio of Cardanol and the material of Colophonium is with 0.3：1～0.8：1 is advisable.
The present invention carries out distribution esterification using two kinds of polyhydric alcohol of glycerol and tetramethylolmethane to Colophonium, purpose is the starlike macromolecular structure to form uniqueness, when glycerol and tetramethylolmethane are simultaneously used for being esterified, its different proportion properties of product are affected very big, when the amount ratio of glycerol and the material of tetramethylolmethane is with 0.5：1～3：When 1, the product that the indices such as viscosity, normal heptane value and color and luster can reach requirement is obtained.
When carrying out distribution esterification to Colophonium using two kinds of polyhydric alcohol of glycerol and tetramethylolmethane, if esterification temperature is higher than 270 DEG C, response speed is too fast, and the strand of product easily disconnects at this temperature, makes that the viscosity of product is low, and color and luster is deeper；If esterification temperature is less than 240 DEG C, reacted slow, the response time is long, and acid number is not easy to lower, not exclusively, viscosity is low, and acid number is big for product reaction；Esterification time is also had an impact to properties of product, and the response time is long, and product viscosity no longer changes after increasing to certain value substantially, and acid number is low；Response time is short, and the viscosity of product is high, and acid number is big, and oil-soluble is poor；Esterification temperature is advisable with 255-265 DEG C, time 4-6 hour.
Concrete preparation process is shown in embodiment 1-4.
Embodiment 1
Weigh 600g Colophonium, 70g Oleum Verniciae fordii to be added in 1000mL there-necked flasks, heating melting is opened stirring and adds 200g Cardanol, 1g magnesium oxide；120 DEG C of addition 70g paraformaldehydes are down to, are reacted 4 hours at 112-116 DEG C；It is warming up to 190 DEG C, 6g cis-butenedioic anhydrides are added to be incubated 15 minutes, it is warming up to 220 DEG C, 30g glycerol is added, 1 hour is incubated, is warming up to 230 DEG C and adds 25g tetramethylolmethanes, insulation 1 hour, 28 mgKOH/g of acid value is measured by sampling within 3 hours in 260 ± 5 DEG C of insulations, viscosity 6800mpa.s/25 DEG C is decompressed to 300-400mmHg and distills 1 hour；After testing, 164 DEG C of product softening point, 19.5 mgKOH/g of acid value, viscosity 8800mpa.s/25 DEG C, normal heptane value 5.6ml/2g.
Embodiment 2
Weigh 600g Colophonium, 70g Oleum Verniciae fordii to be added in 1000mL there-necked flasks, heating melting is opened stirring and adds 220g Cardanol, 1g magnesium oxide；120 DEG C of addition 80g paraformaldehydes are down to, are reacted 4 hours at 112-116 DEG C；It is warming up to 190 DEG C, 6g cis-butenedioic anhydrides are added to be incubated 15 minutes, it is warming up to 220 DEG C, 30g glycerol is added, 1 hour is incubated, is warming up to 230 DEG C and adds 25g tetramethylolmethanes, insulation 1 hour, 25 mgKOH/g of acid value is measured by sampling within 3 hours in 260 ± 5 DEG C of insulations, viscosity 7500mpa.s/25 DEG C is decompressed to 300-400mmHg and distills 1 hour；After testing, 167 DEG C of product softening point, 16.8 mgKOH/g of acid value, viscosity 10600mpa.s/25 DEG C, normal heptane value 5.8ml/2g.
Embodiment 3
Weigh 550g Colophonium, 90g Oleum Verniciae fordii to be added in 1000mL there-necked flasks, heating melting is opened stirring and adds 170g Cardanol, 2g magnesium oxide；120 DEG C of addition 60g paraformaldehydes are down to, are reacted 4 hours at 112-116 DEG C；It is warming up to 190 DEG C, 5g cis-butenedioic anhydrides are added to be incubated 15 minutes, it is warming up to 220 DEG C, 50g glycerol is added, 1 hour is incubated, is warming up to 230 DEG C and adds 30g tetramethylolmethanes, insulation 1 hour, 27 mgKOH/g of acid value is measured by sampling within 3 hours in 260 ± 5 DEG C of insulations, viscosity 6500mpa.s/25 DEG C is decompressed to 300-400mmHg and distills 1 hour；After testing, 162 DEG C of product softening point, 20.5 mgKOH/g of acid value, viscosity 8300mpa.s/25 DEG C, normal heptane value 5.4ml/2g.
Embodiment 4
Weigh 580g Colophonium, 50g Oleum Verniciae fordii to be added in 1000mL there-necked flasks, heating melting is opened stirring and adds 240g Cardanol, 3g magnesium oxide；120 DEG C of addition 100g paraformaldehydes are down to, are reacted 4 hours at 112-116 DEG C；It is warming up to 190 DEG C, 10g cis-butenedioic anhydrides are added to be incubated 15 minutes, it is warming up to 220 DEG C, 20g glycerol is added, 1 hour is incubated, is warming up to 230 DEG C and adds 20g tetramethylolmethanes, insulation 1 hour, 28 mgKOH/g of acid value is measured by sampling within 3 hours in 260 ± 5 DEG C of insulations, viscosity 6700mpa.s/25 DEG C is decompressed to 300-400mmHg and distills 1 hour；After testing, 164 DEG C of product softening point, 19.7 mgKOH/g of acid value, viscosity 8500mpa.s/25 DEG C, normal heptane value 5.5ml/2g.
Above 4 embodiments of the present invention are described in detail, but the content is only presently preferred embodiments of the present invention, it is impossible to be considered as limiting the practical range of the present invention.All impartial changes that is made according to the present patent application scope and improvement etc., still all should belong within the patent covering scope of the present invention.
Claims (10)
1. one-step method environmental protection type resin, it is characterised in that including Colophonium, Oleum Verniciae fordii, Cardanol, paraformaldehyde, glycerol, tetramethylolmethane, cis-butenedioic anhydride, magnesium oxide, each component is consisted of by mass fraction：Colophonium 55-60 parts, Oleum Verniciae fordii 5-10 parts, Cardanol 15-25 parts, paraformaldehyde 5-10 parts, glycerol 2-5 parts, tetramethylolmethane 2-3 parts, cis-butenedioic anhydride 0.5-1 parts, catalyst 0.1-0.5 parts.
2. one-step method environmental protection type resin according to claim 1, it is characterised in that：Each component is consisted of by more high quality number：60 parts of Colophonium, 7 parts of Oleum Verniciae fordii, 22 parts of Cardanol, 8 parts of paraformaldehyde, 3 parts of glycerol, 2.5 parts of tetramethylolmethane, 0.6 part of cis-butenedioic anhydride, 0.1 part of catalyst.
3. one-step method environmental protection type resin according to claim 1, it is characterised in that：The Cardanol adopts pure natural plant extract, and the degree of polymerization of the paraformaldehyde is 8-12.
4. one-step method environmental protection type resin according to claim 1, it is characterised in that：The catalyst is magnesium oxide.
5. one-step method environmental protection type resin according to claim 1, it is characterised in that：The amount of the magnesium oxide accounts for the 0.2-1.5% of Colophonium consumption.
6. one-step method environmental protection type resin according to claim 1, it is characterised in that：The Cardanol is 1 with the ratio of the amount of the material of paraformaldehyde：1.6～1：2.5.
7. the preparation technology of one-step method environmental protection type resin, it is characterised in that comprise the following steps：
（1）Colophonium, Oleum Verniciae fordii are heated to melting, in the Colophonium for melting, add Cardanol and paraformaldehyde, add catalyst control temperature to make phenol formaldehyde condensation, then additive reaction is carried out with Colophonium；
（2）To the step（1）Product in add cis-butenedioic anhydride to carry out D-A reactions, increase the space structure of resin；
（3）To the step（2）Product in add glycerol, tetramethylolmethane to carry out esterification, reaction controlling at 255 DEG C -265 DEG C, after reaction 4 hours, vacuum distillation, you can.
8. the preparation technology of one-step method environmental protection type resin according to claim 7, it is characterised in that：The step（1）In, Cardanol is 110 DEG C -116 DEG C with the more excellent condensation temp of paraformaldehyde, Cardanol：The amount ratio of the more excellent material of Colophonium is 0.3：1～0.8：1.
9. the preparation technology of one-step method environmental protection type resin according to claim 7, it is characterised in that：The step（3）In, glycerol is 0.5 with the amount ratio of the more excellent material of tetramethylolmethane：1～3：1, the more excellent time 4-6 hours of esterification.
10. the preparation technology of one-step method environmental protection type resin according to claim 7, it is characterised in that：The step（3）In, gained resin viscosity >=6000mpa.s/25 DEG C, acid number≤25mgKOH/g, normal heptane value >=5 ml/2g are as qualified.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110452343A (en) * | 2019-08-12 | 2019-11-15 | 德庆华彩合成树脂有限公司 | A kind of environment-friendly type rosin modified phenolic resin and preparation method thereof |
| CN110578261A (en) * | 2019-09-11 | 2019-12-17 | 苏州联胜化学有限公司 | Polyester type terylene anti-sticking soaping agent and preparation method thereof |
| CN115181449A (en) * | 2022-08-23 | 2022-10-14 | 潞安化工集团有限公司 | High-quality easy-storage printing ink resin and preparation method thereof |
-
2015
- 2015-09-08 CN CN201510563314.7A patent/CN106496480A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452343A (en) * | 2019-08-12 | 2019-11-15 | 德庆华彩合成树脂有限公司 | A kind of environment-friendly type rosin modified phenolic resin and preparation method thereof |
| CN110578261A (en) * | 2019-09-11 | 2019-12-17 | 苏州联胜化学有限公司 | Polyester type terylene anti-sticking soaping agent and preparation method thereof |
| CN110578261B (en) * | 2019-09-11 | 2021-11-23 | 苏州联胜化学有限公司 | Polyester type terylene anti-sticking soaping agent and preparation method thereof |
| CN115181449A (en) * | 2022-08-23 | 2022-10-14 | 潞安化工集团有限公司 | High-quality easy-storage printing ink resin and preparation method thereof |
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Application publication date: 20170315 |