CN103113598B - Preparation method of anionic rosin trimethylolpropane ester emulsion - Google Patents

Preparation method of anionic rosin trimethylolpropane ester emulsion Download PDF

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CN103113598B
CN103113598B CN201310076859.6A CN201310076859A CN103113598B CN 103113598 B CN103113598 B CN 103113598B CN 201310076859 A CN201310076859 A CN 201310076859A CN 103113598 B CN103113598 B CN 103113598B
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rosin
anionic
temperature
aqueous solution
trimethylolpropane
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CN103113598A (en
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叶旗
周卓瑜
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WUZHOU FEIZHUOLIN PRODUCTS INDUSTRIAL CO.,LTD.
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Abstract

The invention discloses a preparation method of an anionic rosin trimethylolpropane ester emulsion, and relates to the technical field of chemical industry. The preparation method comprises the following steps of: firstly, adding rosin, trimethylolpropane and a catalyst E to a reactor, mixing under the protection of nitrogen, then increasing the temperature, and carrying out esterification reaction twice to obtain rosin trimethylolpropane ester, mixing and reacting a sodium hydroxide aqueous solution of which the content is 50% and an additive R aqueous solution of which the content is 30 to 50%, adjusting the pH value of a mixture of the sodium hydroxide aqueous solution and the additive R aqueous solution by using sodium hydrogen sulfate to obtain an anionic polymer rosin emulsifier, and carrying out reaction on the anionic polymer rosin emulsifier and rosin trimethylolpropane ester, thus obtaining the anionic rosin trimethylolpropane ester emulsion. In comparison with the prior art, the anionic rosin trimethylolpropane ester emulsion is small in colloidal particles, difficult in agglomeration, less in foamability, stable in coating, and capable of keeping a good viscous force while effectively improving the initial viscous force and the stripping strength of an adhesive, and meets customer requirements.

Description

The preparation method of anionic rosin trihydroxymethylpropanyl ester emulsion
Technical field
The present invention relates to chemical technology field, especially a kind of preparation method of anionic rosin trihydroxymethylpropanyl ester emulsion.
Background technology
The rosin of China is produced and leading status is being captured in rosin deep processing in the world always, flourish along with Gum Rosin industry, the various product of Gum Rosin has been widely used in the industries such as tackiness agent, coating, papermaking, ink, rubber, batik, food.But because the tempo of recent domestic petroleum resin is very fast, starting material source due to petroleum resin is subject to seasonal effect less again, acquisition cost is relatively low, causes petroleum resin in price, to have larger advantage, thereby has impacted original market of Gum Rosin.In recent years again at a time when world economy depressed makes rosin deep processing industry be subject to a certain extent strike.But we have also seen the advantage place of Gum Rosin, from overall performance, Gum Rosin is more extensive than petroleum resin application, and effect is more superior.The raw material sources of Gum Rosin are in renewable resources rosin, at present China's pine tree resin tapping amount only reach that existing pine tree can resin tapping amount 50%, the relatively day by day exhausted more aobvious advantage of petroleum resources.From long term growth prospect, rosin and deep processing industry thereof meet the ambitious goal of Sustainable development, more have good development prospect.
Market of Adhesives both domestic and external, relates to the packing of pencil, books customized, and furniture bonding, all tackiness agent are all lived closely bound uply with us substantially, are directly connected to our health.And inflammable, explosive, volatile, the toxic solvents such as the containing benezene that existing tackiness agent has, ester class, ketone, and the rosin milk of tackiness agent can not take into account each performance index, and foaming is large, little to hard water and temperature tolerance, easily cohesion, micelle is large, is coated with unstable.
Summary of the invention
The preparation method who the invention provides a kind of anionic rosin trihydroxymethylpropanyl ester emulsion, it can solve existing rosin milk can not take into account each performance index, and foaming is large, little to hard water and temperature tolerance, easily cohesion, micelle is large, is coated with unsettled problem.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
The preparation method of anionic rosin trihydroxymethylpropanyl ester emulsion of the present invention, its preparation process is as follows:
A, in reactor, add rosin, TriMethylolPropane(TMP) and catalyzer E, the weight ratio of TriMethylolPropane(TMP) and rosin is 1.2-1.6:10, the weight ratio of catalyzer E and rosin is 0.1-0.25:100, mixed in 180 ℃ under the protection of nitrogen, then be warmed up to 210 ℃, and be incubated 2 hours and carry out partial esterification reaction, after 2 hours finish, be warmed up to again 250 ℃-255 ℃, and be incubated and within 5-8 hour, carry out esterification, obtain rosin trihydroxymethylpropanyl ester, in insulation, check softening temperature and the acid number whether color of resin is deepened and detected resin after 5 hours;
The auxiliary agent R aqueous solution that the aqueous sodium hydroxide solution that B, formulation content are 50% and content are 30-50%, under agitation condition, the mode that the weight ratio of aqueous sodium hydroxide solution and the auxiliary agent R aqueous solution of take is 1:5 adds the auxiliary agent R aqueous solution to aqueous sodium hydroxide solution, after mixed, stir 60 minutes, reaction finishes rear dropping sodium pyrosulfate, regulates the pH value of mixed solution, makes pH value be controlled at 7-10, use cooling water circulation control temperature of reaction, adjusting temperature is 70 ℃-75 ℃ simultaneously; Adjustment completes, and filters, and obtains anionic polymer rosin emulsifying agent;
C, regulate the temperature of reactor under the condition of 100 ℃-105 ℃, the rosin trihydroxymethylpropanyl ester of the anionic polymer rosin emulsifying agent of B step gained and A step gained be take to the ratio that weight ratio is 1.5-2:10 and to rosin trihydroxymethylpropanyl ester, progressively add anionic polymer rosin emulsifying agent, be uniformly mixed 20 minutes, cool to 97 ℃-100 ℃, add again 90 ℃ of hot soft water to make resin phase inversion, after phase inversion, progressively add 90 ℃ of hot soft water to calculate and adjust emulsion solid content, adjust complete, use cooling water temperature, temperature of cooling water and the still temperature temperature difference are no more than 30 ℃, obtain anionic rosin trihydroxymethylpropanyl ester emulsion.
In technique scheme, scheme is more specifically: described catalyzer E is esterifying catalyst, and described esterifying catalyst is one or more the mixture in phosphoric acid, Hypophosporous Acid, 50, calcium propionate, calcium hydroxide, calcium acetate, Quilonum Retard, zinc oxide and magnesium oxide; Described auxiliary agent R is polymeric surface active agent, and described polymeric surface active agent is one or more the mixture in Styrene And Chloroalkyl Acrylates salt copolymer, methacrylic acid Soxylat A 25-7-acrylate multipolymer, methyl thiazolinyl polyethenoxy ether, isopentene group polyethers, poly glycol monomethyl ether (CH3O (CH2CH2O) nH) and allyl polyethenoxy ether (CH2=CHCH2O (CH2CH2O) nH).
Owing to adopting technique scheme, the present invention has following beneficial effect:
Because the present invention be take rosin and TriMethylolPropane(TMP) prepare anionic rosin trihydroxymethylpropanyl ester emulsion with the emulsification of anionic polymer rosin emulsifying agent after raw material is carried out esterification, make product emulsion foaminess little, large to hard water and temperature tolerance, be difficult for cohesion, micelle is little, and coating is stable; Use compared with the rosin trihydroxymethylpropanyl ester of high softening-point as basic resin, make emulsion keep the good viscous force of holding when increasing substantially the initial bonding strength of tackiness agent and peeling force, the rosin milk that has solved original adhesive industry can not be taken into account the shortcoming of each performance index.
Embodiment
Below in conjunction with specific examples, the invention will be further described:
Embodiment 1-
Its making step is:
A, in reactor, add 5400 kilograms of rosin, 648 kilograms of TriMethylolPropane(TMP)s and 5.4 kilograms of phosphoric acid as esterifying catalyst and zinc oxide, mixed in 180 ℃ under the protection of nitrogen, then be warmed up to 210 ℃, and be incubated 2 hours and carry out partial esterification reaction, after 2 hours finish, be warmed up to again 250 ℃-255 ℃, and be incubated and within 5-8 hour, carry out esterification, obtain rosin trihydroxymethylpropanyl ester, in insulation, check softening temperature and the acid number whether color of resin is deepened and detected resin after 5 hours; In the situation that color is not deepened, softening temperature and acid number more approach the center of span of control, and rosin TriMethylolPropane(TMP) resin is unreasonable thinks;
The aqueous sodium hydroxide solution of B, formulation content 50% and content are the Styrene And Chloroalkyl Acrylates salt copolymer as polymeric surface active agent of 30-50%, under agitation condition, the mode that the weight ratio of aqueous sodium hydroxide solution and Styrene And Chloroalkyl Acrylates salt copolymer of take is 1:5 adds Styrene And Chloroalkyl Acrylates salt copolymer to aqueous sodium hydroxide solution, after mixed, stir 60 minutes, reaction finishes rear dropping sodium pyrosulfate, regulate the pH value of mixed solution, make pH value be controlled at 7-10, use cooling water circulation control temperature of reaction, adjusting temperature is 70 ℃-75 ℃ simultaneously; Adjustment completes, and filters, and obtains anionic polymer rosin emulsifying agent;
C, regulate the temperature of reactor under the condition of 100 ℃-105 ℃, the rosin trihydroxymethylpropanyl ester of the anionic polymer rosin emulsifying agent of B step gained and A step gained be take to the ratio that weight ratio is 1.5-2:10 and to rosin trihydroxymethylpropanyl ester, progressively add anionic polymer rosin emulsifying agent, be uniformly mixed 20 minutes, cool to 97 ℃-100 ℃, add again 90 ℃ of hot soft water to make resin phase inversion, after phase inversion, progressively add 90 ℃ of hot soft water to calculate and adjust emulsion solid content, adjust complete, use cooling water temperature, temperature of cooling water and the still temperature temperature difference are no more than 30 ℃, obtain anionic rosin trihydroxymethylpropanyl ester emulsion.
Embodiment 2
Its making step is:
A, in reactor, add the calcium hydroxide as esterifying catalyst and the magnesium oxide of 5400 kilograms of rosin, 864 kilograms of TriMethylolPropane(TMP)s and 13.5 kilograms, mixed in 180 ℃ under the protection of nitrogen, then be warmed up to 210 ℃, and be incubated 2 hours and carry out partial esterification reaction, after 2 hours finish, be warmed up to again 250 ℃-255 ℃, and be incubated and within 5-8 hour, carry out esterification, obtain rosin trihydroxymethylpropanyl ester, in insulation, check softening temperature and the acid number whether color of resin is deepened and detected resin after 5 hours; In the situation that color is not deepened, softening temperature and acid number more approach the center of span of control, and rosin TriMethylolPropane(TMP) resin is unreasonable thinks;
B, the aqueous sodium hydroxide solution of formulation content 50% and content are the Soxylat A 25-7-acrylate multipolymer of the methacrylic acid as polymeric surface active agent of 30-50%, under agitation condition, the mode that the weight ratio of aqueous sodium hydroxide solution and methacrylic acid Soxylat A 25-7-acrylate multipolymer of take is 1:5 adds methacrylic acid Soxylat A 25-7-acrylate multipolymer to aqueous sodium hydroxide solution, after mixed, stir 60 minutes, reaction finishes rear dropping sodium pyrosulfate, regulate the pH value of mixed solution, make pH value be controlled at 7-10, use cooling water circulation control temperature of reaction simultaneously, adjusting temperature is 70 ℃-75 ℃, adjustment completes, and filters, and obtains anionic polymer rosin emulsifying agent,
C, regulate the temperature of reactor under the condition of 100 ℃-105 ℃, the rosin trihydroxymethylpropanyl ester of the anionic polymer rosin emulsifying agent of B step gained and A step gained be take to the ratio that weight ratio is 1.5-2:10 and to rosin trihydroxymethylpropanyl ester, progressively add anionic polymer rosin emulsifying agent, be uniformly mixed 20 minutes, cool to 97 ℃-100 ℃, add again 90 ℃ of hot soft water to make resin phase inversion, after phase inversion, progressively add 90 ℃ of hot soft water to calculate and adjust emulsion solid content, adjust complete, use cooling water temperature, temperature of cooling water and the still temperature temperature difference are no more than 30 ℃, obtain anionic rosin trihydroxymethylpropanyl ester emulsion.
Anionic rosin trihydroxymethylpropanyl ester emulsion technology index of the present invention is as table one:
Index Scope
Outward appearance White milk sap
Viscosity (30 ℃), mPas 200-800
PH value 7-10
Solids content 58%-62%
Stability Within 180 days, there is not demixing phenomenon

Claims (2)

1. a preparation method for anionic rosin trihydroxymethylpropanyl ester emulsion, is characterized in that: its preparation process is as follows:
A, in reactor, add rosin, TriMethylolPropane(TMP) and catalyzer E, the weight ratio of TriMethylolPropane(TMP) and rosin is 1.2-1.6:10, the weight ratio of catalyzer E and rosin is 0.1-0.25:100, mixed in 180 ℃ under the protection of nitrogen, then be warmed up to 210 ℃, and be incubated 2 hours and carry out partial esterification reaction, after 2 hours finish, be warmed up to again 250 ℃-255 ℃, and be incubated and within 5-8 hour, carry out esterification, obtain rosin trihydroxymethylpropanyl ester, in insulation, check softening temperature and the acid number whether color of resin is deepened and detected resin after 5 hours;
The auxiliary agent R aqueous solution that the aqueous sodium hydroxide solution that B, formulation content are 50% and content are 30-50%, under agitation condition, the mode that the weight ratio of aqueous sodium hydroxide solution and the auxiliary agent R aqueous solution of take is 1:5 adds the auxiliary agent R aqueous solution to aqueous sodium hydroxide solution, after mixed, stir 60 minutes, reaction finishes rear dropping sodium pyrosulfate, regulates the pH value of mixed solution, makes pH value be controlled at 7-10, use cooling water circulation control temperature of reaction, adjusting temperature is 70 ℃-75 ℃ simultaneously; Adjustment completes, and filters, and obtains anionic polymer rosin emulsifying agent;
C, regulate the temperature of reactor under the condition of 100 ℃-105 ℃, the rosin trihydroxymethylpropanyl ester of the anionic polymer rosin emulsifying agent of B step gained and A step gained be take to the ratio that weight ratio is 1.5-2:10 and to rosin trihydroxymethylpropanyl ester, progressively add anionic polymer rosin emulsifying agent, be uniformly mixed 20 minutes, cool to 97 ℃-100 ℃, add again 90 ℃ of hot soft water to make resin phase inversion, after phase inversion, progressively add 90 ℃ of hot soft water to calculate and adjust emulsion solid content, adjust complete, use cooling water temperature, temperature of cooling water and the still temperature temperature difference are no more than 30 ℃, obtain anionic rosin trihydroxymethylpropanyl ester emulsion.
2. the preparation method of anionic rosin trihydroxymethylpropanyl ester emulsion according to claim 1, it is characterized in that: described catalyzer E is esterifying catalyst, described esterifying catalyst is one or more the mixture in phosphoric acid, Hypophosporous Acid, 50, calcium propionate, calcium hydroxide, calcium acetate, Quilonum Retard, zinc oxide and magnesium oxide; Described auxiliary agent R is polymeric surface active agent, and described polymeric surface active agent is any in Styrene And Chloroalkyl Acrylates salt copolymer, methacrylic acid Soxylat A 25-7-acrylate multipolymer.
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