CN106578026A - Waterborne rosin polymer for fruit and vegetable preservative and preparation method thereof - Google Patents
Waterborne rosin polymer for fruit and vegetable preservative and preparation method thereof Download PDFInfo
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- CN106578026A CN106578026A CN201611113303.XA CN201611113303A CN106578026A CN 106578026 A CN106578026 A CN 106578026A CN 201611113303 A CN201611113303 A CN 201611113303A CN 106578026 A CN106578026 A CN 106578026A
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/16—Coating with a protective layer; Compositions or apparatus therefor
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Abstract
The present invention provides a waterborne rosin polymer for a fruit and vegetable preservative and a preparation method thereof. The preparation method comprises the following steps: step one, a polymerization reaction of rosin: the rosin reacts with unsaturated acids to obtain a rosin polymer product; and step two, a salt forming reaction: 20 g of the rosin polymer is weighed, the weighed rosin polymer is ground, the ground rosin polymer is added into a 500 ml four-necked flask, 180 ml of water is added, the temperature of the materials is raised to 50-100 DEG C, a stirring is conducted, an alkali solution is slowly dropped until the rosin polymer is completely dissolved, a pH of the solution is adjusted to be 7-8, and the solution is diluted to an appropriate concentration with water. An acid value of the rosin polymer products is larger than or equal to 150 mg/g, a softening point is larger than or equal to 95 DEG C and a solubility is transparent; and a heavy metal content meets food grade requirements, wherein an arsenic content is less than or equal to 2 ppm and a lead content is less than or equal to 10 ppm. The products are relatively high in molecular weight, good in film-forming performance, and bright and lasting in color and luster.
Description
Technical field
The present invention relates to the preparation and its application of fruit and vegetable fresh-keeping agent, belong to field of food storage.
Background technology
With the development of science and technology, the living standard of people is stepped up, the vegetable water to the production of Various Seasonal different regions
The demand of fruit increasingly increases, and still carry out after fresh fruit and vegetable harvesting the physiological change of complexity, biological change and
Physical change, the cell and tissue of fruit and vegerable proceed breathing and transpiration, it is easy to produce shrinkage, weightlessness, wilting, rotten
Etc. phenomenon, quality and the sale of fruit and vegerable is have impact on.Therefore, preserving fruit and vegetable utilizing is one in vegetable and fruit production, storage and sales section
Individual very important problem.
At present conventional preserving fruit and vegetable utilizing fruit glaze agent has wax, natural resin, oils, lac, morpholine fatty acid salt etc..China
A large amount of morpholine fatty acid salt fruit freshness preserving fruit glaze agents for adopting, be with fossil resources as raw material, exist it is big to oil interdependency,
The shortcoming of poor stability, in European Union into disabling product；The features such as plant source lac has nontoxic, good film-forming property, high transparency,
Early stage is developed to prepare the important source material of preserving fruit and vegetable utilizing fruit glaze agent, but because lac softening point is low, heat stability is poor, membrane is easy
Whiting, and the factor such as substantial appreciation of prices in recent years, limit its popularization and application.With people's pay attention to day by day safe to food,
Plant source preserving fruit and vegetable utilizing fruit glaze agent manifests wide application prospect with its features such as wide, safety is good of originating, and realizes plant source
Commercialization application of the fruit glaze agent on fruit and vegerable is the principal direction of Future Development.Although the research and development of domestic plant source fruit and vegerable fruit glaze agent take
Some progress were obtained, but was totally sought and the application test stage also in rationale, majority was the performance and film forming around film
The research that mechanism is launched, the less merchandized handling for realizing plant source fruit glaze agent.So novel plant source preserving fruit and vegetable utilizing fruit glaze agent
Exploitation seem particularly urgent.
Colophonium is the important natural reproducible woods local product resource of China, and rosin acid contains tricyclic diterpene phenanthrene skeleton, with nothing
Malicious, transparent and good film property and membrane stability, can become the advantage raw material of exploitation preserving fruit and vegetable utilizing fruit glaze agent.
Jing has found that the patent for preparing fruit and vegerable fruit glaze agent using rosin product has to existing document retrieval：1) apply for a patent
Number, 201010185249.6, denomination of invention, a kind of production method of Chinese medicinal refreshing fruit wax, wherein using 1～2% Malaysia pine
Fragrant modified resin aqueous solution, its preparation method is to be esterified maleic rosin and tetramethylolmethane, adds emulsifying agent to carry out emulsifying
Make maleic rosin modified resin aqueous solution.2) number of applying for a patent 201010125141.8, denomination of invention, a kind of milk protein base
Fresh-keeping fruit glaze agent of natural fruit and vegetables and preparation method thereof, has used a certain amount of rosin glyceride, preparation method be by milk protein,
Food lac is added in food stage sodium hydrate aqueous solution, is heated to obtaining fruit glaze agent water phase liquid after 85～110 DEG C of dissolvings；Will
Fruit glaze agent oil phase liquid is obtained after edible vegetable oil, the mixing of rosin glyceride heated and stirred.Oil phase liquid is slowly added to into water phase tank, is protected
80～120 DEG C of temperature is held, machinery emulsification adds sucrose and vitamin C, stirring to mix, add edible ethanol to adjust concentration, filter,
Obtain the fresh-keeping fruit glaze agent of milk protein base.In two above patent, without reference to the preparation method of rosin ester compound, and
Need first then to use rosin ester emulsifying, but, pentalyn and rosin glyceride emulsifying difficulty are larger, should
The introducing of technique not only considerably increases product cost, and the emulsifying product less stable for generating, and shortens antistaling agent product
Shelf-life.3) number of applying for a patent, 97101646.1, denomination of invention, fruit and vegetable fresh-keeping agent and its production method, using 30% or so
Modified natural rosin, be dissolved in ethanol, make biofilm matrix after then mixing with Cera Flava emulsifying.But Colophonium
Film property and brightness are not as good as Colophonium esters product, and consequences for use vegetable gloss duration is poor.4) number of applying for a patent,
201410114124.2, denomination of invention, a kind of abietyl preserving fruit and vegetable utilizing fruit glaze agent and preparation method thereof, by Colophonium and maleic acid
D-A additive reaction, and obtain rosin ester product with the moderately esterified reaction of polyhydric alcohol, the fruit glaze agent gloss and weatherability compared with
It is good, but because the products molecule is less, membrane stability is not good enough.
The content of the invention
The invention aims to overcome weak point of the prior art, there is provided a kind of fruit and vegetable fresh-keeping agent is loose with aqueouss
Fragrant polymer and preparation method thereof, the molecular weight product is higher, and filming performance is good, bright in color persistency, and meets food additive
Plus agent safety requirements.
The present invention is adopted the technical scheme that：A kind of fruit and vegetable fresh-keeping agent aqueouss rosin polymer, with Colophonium and unsaturation
Acid carries out polyreaction and obtains rosin polymer, acid number：>=150mg/g, ring and ball softening point：≥95℃；Rosin polymer with
Alkali salt-forming reaction obtains the aqueous solution of suitable concn, dissolubility in 10% aqueous alkali：It is transparent；Content of beary metal reaches food
Level requirement, wherein, arsenic content≤2ppm, lead content≤10ppm in terms of heavy metal.
Described Colophonium is gum rosin or refined gum rosin.
Described unsaturated acids are any one in maleic acid, fumaric acid, acrylic acid, glutaconate, hexene diacid.
The described fruit and vegetable fresh-keeping agent method of aqueouss rosin polymer is prepared, is comprised the steps：
The first step, the polyreaction of Colophonium：Under nitrogen environment, Colophonium is anti-with unsaturated acids after heating for dissolving in a solvent
Should, reaction stops heating after terminating, vacuum decompression is extremely slipped out without low-boiling-point substance and obtains rosin polymer；
Second step, salt-forming reaction：Rosin polymer adds water intensification stirring and slowly Deca aqueous slkali, until rosin polymer
It is completely dissolved, and adjusts pH value of solution to 7～8, is diluted with water to suitable concentration.
The molal weight proportioning of Colophonium and unsaturated acids is 1：Between 0.5～1.0.
Described initiator be azodiisobutyronitrile, benzoyl peroxide, two tertiary base peroxide, the cumin of peroxidating two,
Any one in hydrogen peroxide.
Described solvent includes aromatic hydrocarbons, aliphatic (acid) ester or aromatic ester.
Described solvent includes any one in benzene, ethyl acetate, tetrahydrofuran.
Reaction temperature is 50～130 DEG C in the first step, and the response time is 10～30 hours.
Initiator amount is the 0.01～2% of rosin quality.
Beneficial effect
1. this product is obtained by the molal weight proportioning of control Colophonium and unsaturated acids to reach control molecular weight product
The product of appropriateness polymerization.
2. this product molecular weight is higher, and filming performance is good, bright in color persistency；
3. the fruit and vegetable fresh-keeping agent of the present invention, can suppress the respiratory intensity of fruit and vegerable, extending the storage period of fruit and vegerable, reduction rotting rate
And loss rate, the quality of fruit and vegerable is improved, increase economic benefit.Simultaneously the fruit and vegetable fresh-keeping agent of the present invention is matched somebody with somebody also with low cost
Side is simple, the advantages of easy to operate.Additionally, the fruit and vegetable fresh-keeping agent component of the present invention is safe and reliable, it is useful and harmless to human body.
Description of the drawings
The relation of the little storing tomato natural law of Fig. 1 and weight-loss ratio；
The relation of the little storing tomato natural law of Fig. 2 and rotting mechanism；
The relation of the little storing tomato natural law of Fig. 3 and respiratory intensity；
The GPC spectrograms of Fig. 4 Colophonium raw materials；
The GPC spectrograms of the product of the gained of Fig. 5 embodiments 1；
The GPC spectrograms of the products obtained therefrom of Fig. 6 comparative examples 2.
Specific embodiment
A kind of fruit and vegetable fresh-keeping agent preparation method of aqueouss rosin polymer, with Colophonium and unsaturated acids polyreaction is carried out
Rosin polymer is obtained, then rosin polymer and alkaline reaction are configured to into the aqueous antistaling liquid of suitable concn.Rosin polymer
Acid number be more than 150mg/g, softening point (ring and ball method) >=95 DEG C, dissolubility (10%KOH aqueous solutions) is transparent；Content of beary metal
Food stage requirement is reached, wherein, arsenic content≤2ppm counts weight tenor≤10ppm with lead；It is higher with molecular weight, film forming
Performance is good, bright in color persistently, good water solubility, the advantages of meet food additive hygienic requirements.Below for abietic acid in Colophonium with
Polymer formulae obtained by maleic acid polymerization.
The structural formula of the polymer of abietic acid and maleic acid
Described Colophonium is common gum rosin or refined gum rosin.
Described unsaturated acids are any one in maleic acid, fumaric acid, acrylic acid, glutaconate, hexadienoic acid etc..
The described fruit and vegetable fresh-keeping agent method of aqueouss rosin polymer is prepared, is comprised the steps：
The first step, the polyreaction of Colophonium：Colophonium 100g is weighed, 80～160ml of solvent is added, leads to nitrogen, heating.Work as temperature
Degree rises to 50～130 DEG C or so, is slowly added into the molal weight proportioning of unsaturated acids, Colophonium and unsaturated acids 1：0.5～1：
1.0 between；Addition accounts for the initiator of rosin quality 0.01～2%.Reaction stops heating after 10～30 hours, and vacuum decompression is to nothing
Slip out without low-boiling-point substance, obtain rosin polymer product.
Second step, salt-forming reaction：Rosin polymer 20g is weighed, is added in 500ml reaction flasks after grinding, and added
180ml water, is warming up between 50～100 DEG C.Stirring and slowly Deca aqueous slkali, until rosin polymer is completely dissolved, are adjusted
PH value of solution is diluted with water to suitable concentration to 7～8.
The molal weight proportioning of Colophonium and unsaturated acids is preferably 1 in the first step：0.6～1：Between 0.8.
Initiator is that azodiisobutyronitrile, benzoyl peroxide, two tertiary base peroxide, peroxidating two are withered in the first step
Any one of tender tea leaves, hydrogen peroxide etc., consumption is preferably 0.1～1%.
Reaction temperature is best 60～80 DEG C in the first step.
Lye type in second step is organic base or inorganic base, including choline, KOH, NaOH etc..
Reaction temperature is between 50～100 DEG C in second step.
Solvent used by polyreaction of the present invention can dissolve raw material and product, the aromatic hydrocarbons such as including benzene, aliphatic (acid) ester or fragrance
Ester, such as ethyl acetate, tetrahydrofuran etc..
Embodiment 1
A kind of preparation of aqueouss rosin polymer of fruit and vegetable fresh-keeping agent, comprises the steps：
The first step, the polyreaction of Colophonium：Resin 100g is weighed, ethyl acetate 100ml is added, leads to nitrogen, stirred,
75 DEG C or so are warming up to, 25.7g maleic acids and 2g initiator azodiisobutyronitriles is slowly added into.After reaction 27 hours, stop adding
Heat, vacuum decompression obtains rosin polymer product to slipping out without low-boiling-point substance.
Second step, salt-forming reaction：Above-mentioned rosin polymer product 20g is weighed, is ground and is added in 500ml reaction flasks, and
180ml water is added, 80 DEG C are warming up to.Stirring and slowly Deca aqueous choline base solution, until rosin polymer is completely dissolved, are adjusted molten
Liquid pH to 7～8.It is diluted with water to suitable concentration.
Rosin polymer product, acid number, 186.1mg/g；Softening point (ring and ball method), 106.0 DEG C；Dissolubility (10% choline
Aqueous solution)：It is transparent；Arsenic content≤2ppm, lead content (in terms of heavy metal)≤10ppm.
Embodiment 2
A kind of preparation of aqueouss rosin polymer of fruit and vegetable fresh-keeping agent, comprises the steps：
The first step, the polyreaction of Colophonium：Colophonium 100g is weighed, tetrahydrofuran 100ml is added, leads to nitrogen, stirring heats up
To 75 DEG C or so, 21.9g maleic acids and 2g initiator benzoyl peroxides are slowly added into.After reaction 27 hours, stop heating, very
Sky is decompressed to and is slipped out without low-boiling-point substance, obtains rosin polymer product.
Second step, salt-forming reaction：Above-mentioned rosin polymer 20g is weighed, is ground and is added in 500ml reaction flasks, and added
180ml water, is warming up to 80 DEG C.Stirring and slowly Deca KOH aqueous solution, until Colophonium is completely dissolved, and adjust pH value of solution to 7～
8.It is diluted with water to suitable concentration.
Rosin polymer product, acid number, 201.3mg/g；Softening point (ring and ball method), 99.0 DEG C；Dissolubility (10%KOH water
Solution)：It is transparent；Arsenic content≤2ppm, lead content (in terms of heavy metal)≤10ppm.
Embodiment 3
A kind of preparation of aqueouss rosin polymer of fruit and vegetable fresh-keeping agent, comprises the steps：
The first step, the polyreaction of Colophonium：Colophonium 100g is weighed, dimethylbenzene 100ml is added, leads to nitrogen, stirring is warming up to
100 DEG C or so, it is slowly added into 16.0g acrylic acid and 1.5g initiator azodiisobutyronitriles.Reaction 25 hours, stops heating, very
Sky is decompressed to and is slipped out without low-boiling-point substance, obtains rosin polymer product.
Second step, into salt：Above-mentioned Colophonium product 20g is weighed, is ground and is added in 500ml four-hole boiling flasks, and add 180ml
Water, reflux condensation mode is warming up to 80 DEG C.Stirring and slowly Deca KOH aqueous solution, until Colophonium is completely dissolved, and adjust pH value of solution
To 7～8.Pour out after cooling, be diluted with water to suitable concentration.
Rosin polymer product, acid number, 190.1mg/g；Softening point (ring and ball method), 105.0 DEG C；Dissolubility (10%KOH water
Solution)：It is transparent；Arsenic content≤2ppm, lead content (in terms of heavy metal)≤10ppm.
Comparative example 1
A kind of preparation of aqueouss rosin polymer of fruit and vegetable fresh-keeping agent, comprises the steps：
The first step, the polyreaction of Colophonium：Resin 100g is weighed, ethyl acetate 100ml is added, leads to nitrogen, stirred,
100 DEG C or so are warming up to, 39g maleic acids and 2.0g initiator azodiisobutyronitriles is slowly added into.Reaction 10 hours, occurs sudden and violent
It is poly-, stop heating, obtain rosin polymer product.
Second step, salt-forming reaction：Above-mentioned rosin polymer 20g is weighed, is ground and is added in 500ml reaction flasks, and added
180ml water, is warming up to 80 DEG C.Stirring and slowly Deca KOH aqueous solution, until Colophonium is completely dissolved, adjust pH value of solution to 7～8.
It is diluted with water to suitable concentration.
Rosin polymer product, acid number：194.2mg/g；Softening point (ring and ball method)：153.0℃；Dissolubility (10%KOH water
Solution)：It is transparent；Content of beary metal reaches food stage requirement, wherein, arsenic content≤2ppm, lead content (in terms of heavy metal)≤
10ppm。
Comparative example 2
The granted patent preparation method (201410114124.2) of Abietyl modified product " a kind of preserving fruit and vegetable utilizing fruit glaze agent with ",
Comprise the steps：
The first step, the D-A additive reaction of Colophonium.The gum rosin of 100g is heated to into 160 DEG C or so meltings, stirring is lower to be added
20g acrylic acid, is slowly ramped to 220 DEG C, reacts 4 hours, obtains acrylic acid rosin.
Second step, moderately esterified reaction.By 100g acrylic acid rosins, 220 DEG C are heated to, are slowly added into 10g seasons penta
Tetrol and 5g polyethylene glycol 200s, 0.2g nano-ZnO catalyst reacts 2 hours, obtains rosin ester compound.
3rd step, post processing.Saturated vapor is passed through the reactor for filling rosin ester compound, steaming 1 hour is persistently blown, so
Afterwards vacuum decompression 1 hour, obtains fruit glaze agent product.
Product acid number：155mg/g；Softening point (ring and ball method)：111℃；Dissolubility (50% ethanol solution)：It is transparent；Arsenic contains
Amount≤2ppm, lead content (in terms of heavy metal)≤10ppm.
Application Example
The product that application experiment is adopted product (a) obtained in the embodiment of the present invention 1, product obtained in comparative example 2
B (), using water blanks (c) as control, by product a, b is configured to the fresh-keeping liquid of suitable concn.
Picking is uniform in size, Maturity, and coloring is basically identical, and the lossless fresh little Fructus Lycopersici esculenti for injuring disease pest is test material,
First cleaned, packet after drying is immersed in fresh-keeping liquid a, b, in c, after about 40s, take out nature and dry.Determined once per 2 days
Weight-loss ratio, rotting mechanism and respiratory intensity, Fig. 1, Fig. 2 and Fig. 3 are experimental result.
As seen from Figure 1, with the increase of natural law, weight-loss ratio becomes larger.And when using product a of the present invention, little kind
The rate of body weight gain of eggplant is relatively low, and effect is best.
As seen from Figure 2, with the increase of natural law, rotting mechanism becomes larger, and when using product a of the present invention, it is little
The rotting mechanism of Fructus Lycopersici esculenti is relatively low, and effect is best.
As seen from Figure 3, little Fructus Lycopersici esculenti is on a declining curve in storage period respiratory intensity, wherein during using product a, little Fructus Lycopersici esculenti
Respiratory intensity is minimum, and effect is best.
Molecular weight test is carried out to raw material and product using GPC method, as a result such as Fig. 4, shown in 5,6.Fig. 4 Colophonium raw materials
GPC figure only one of which peak, weight average molecular weight is 295.
Fig. 5 is the GPC spectrograms of the products obtained therefrom of embodiment 1, and product G PC figure has two peaks, and first peak is rosin polymer
Peak, weight average molecular weight is 8527, and accounting is 32.86%, and second peak is the peak of the rosin acid not reacted, and weight is equal
Molecular weight is 267, and accounting is 67.14%.
Fig. 6 is the GPC spectrograms of the products obtained therefrom of comparative example 2, and product G PC figure has two peaks, and first peak is rosin ester
The peak of compound, weight average molecular weight is 1523, and second peak is the peak of rosin acid.
By Fig. 4,5,6 is visible, and product of the present invention has relatively large molecular weight, so having preferable fresh-keeping effect.
Claims (10)
1. a kind of fruit and vegetable fresh-keeping agent aqueouss rosin polymer, it is characterised in that carry out polyreaction with Colophonium and unsaturated acids
Obtain rosin polymer, acid number：>=150mg/g, ring and ball softening point：≥95℃；Rosin polymer is obtained with alkali salt-forming reaction
The aqueous solution of suitable concn, dissolubility in 10% aqueous alkali：It is transparent；Content of beary metal reaches food stage requirement, wherein, arsenic
Content≤2ppm, lead content≤10ppm in terms of heavy metal.
2. fruit and vegetable fresh-keeping agent according to claim 1 aqueouss rosin polymer, it is characterised in that described Colophonium is fat
Colophonium or refined gum rosin.
3. fruit and vegetable fresh-keeping agent according to claim 1 aqueouss rosin polymer, it is characterised in that described unsaturated acids
For any one in maleic acid, fumaric acid, acrylic acid, glutaconate, hexene diacid.
4. the method for preparing arbitrary described fruit and vegetable fresh-keeping agent aqueouss rosin polymer in claims 1 to 3, its feature exists
In comprising the steps：
The first step, the polyreaction of Colophonium：Under nitrogen environment, Colophonium in a solvent after heating for dissolving with unsaturated acids reaction, instead
Stop heating after should terminating, vacuum decompression is extremely slipped out without low-boiling-point substance and obtains rosin polymer；
Second step, salt-forming reaction：Rosin polymer adds water intensification stirring and slowly Deca aqueous slkali, until rosin polymer is complete
Dissolving, and pH value of solution is adjusted to 7～8, it is diluted with water to suitable concentration.
5. the method for preparing fruit and vegetable fresh-keeping agent aqueouss rosin polymer according to claim 4, it is characterised in that Colophonium
With the molal weight proportioning of unsaturated acids 1：Between 0.5～1.0.
6. the method for preparing fruit and vegetable fresh-keeping agent aqueouss rosin polymer according to claim 4, it is characterised in that described
Initiator be azodiisobutyronitrile, benzoyl peroxide, two tertiary base peroxide, the cumin of peroxidating two, hydrogen peroxide in
Any one.
7. the method for preparing fruit and vegetable fresh-keeping agent aqueouss rosin polymer according to claim 4, it is characterised in that described
Solvent include aromatic hydrocarbons, aliphatic (acid) ester or aromatic ester.
8. the method for preparing fruit and vegetable fresh-keeping agent aqueouss rosin polymer according to claim 4, it is characterised in that described
Solvent include benzene, ethyl acetate, tetrahydrofuran in any one.
9. the method for preparing fruit and vegetable fresh-keeping agent aqueouss rosin polymer according to claim 4, it is characterised in that first
Reaction temperature is 50～130 DEG C in step, and the response time is 10～30 hours.
10. the method for preparing fruit and vegetable fresh-keeping agent aqueouss rosin polymer according to claim 4, it is characterised in that draw
Agent consumption is sent out for the 0.01～2% of rosin quality.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175522A (en) * | 2020-09-18 | 2021-01-05 | 云南鑫煌新材料有限公司 | Preparation process and method of water-based coating agent |
| CN113367188A (en) * | 2021-05-21 | 2021-09-10 | 江苏派乐滋食品有限公司 | Preparation method of rosin-based coating agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103828912A (en) * | 2014-03-25 | 2014-06-04 | 中国林业科学研究院林产化学工业研究所 | Rosin-based fruit and vegetable fresh-keeping coating agent and preparation method thereof |
-
2016
- 2016-12-06 CN CN201611113303.XA patent/CN106578026B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103828912A (en) * | 2014-03-25 | 2014-06-04 | 中国林业科学研究院林产化学工业研究所 | Rosin-based fruit and vegetable fresh-keeping coating agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 詹益兴主编: "《绿色化学化工第2集》", 30 June 2002 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112175522A (en) * | 2020-09-18 | 2021-01-05 | 云南鑫煌新材料有限公司 | Preparation process and method of water-based coating agent |
| CN113367188A (en) * | 2021-05-21 | 2021-09-10 | 江苏派乐滋食品有限公司 | Preparation method of rosin-based coating agent |
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