CN106590468A - High-temperature cured type esterification modified cassava starch adhesive and preparation method thereof - Google Patents
High-temperature cured type esterification modified cassava starch adhesive and preparation method thereof Download PDFInfo
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- CN106590468A CN106590468A CN201710094349.XA CN201710094349A CN106590468A CN 106590468 A CN106590468 A CN 106590468A CN 201710094349 A CN201710094349 A CN 201710094349A CN 106590468 A CN106590468 A CN 106590468A
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- 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
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
- C09J103/06—Esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- Polymers & Plastics (AREA)
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Abstract
The invention provides a high-temperature cured type esterification modified cassava starch adhesive and a preparation method thereof and belongs to the technical field of adhesive preparation. At present, raw materials of adhesives generally used in the wood industry are non-renewable. The high-temperature cured type esterification modified cassava starch adhesive is mainly prepared from, by weight, 80-100 parts of modified cassava starch adhesive, 7-12 parts of isocyanate, 0.5-1.5 parts of antioxygen, 0.5-2 parts of flame retardant, 0.02-0.2 part of light stabilizer and 0.5-1 part of ultraviolet light absorber, wherein the modified cassava starch adhesive comprises cassava starch, polyvinyl alcohol, sodium dodecyl sulfate and dodecenyl succinic anhydride. The high-temperature cured type esterification modified cassava starch adhesive is moderate in viscosity, stable in storing and slow in layering. The preparation process is simple and easy to operate. The consumed time is short. The high-temperature cured type esterification modified cassava starch adhesive is excellent in water resistant performance and bonding strength, and industrial production is likely to be realized.
Description
Technical field
The invention belongs to adhesive preparing technical field, and in particular to a kind of hot setting type esterification modification Tapioca adhesive
Stick and preparation method thereof.
Background technology
The adhesive for commonly using in timber industry at present is the conjunction prepared by ureaformaldehyde, phenolic aldehyde, melamine resin
Into macromolecule adhesive, its raw material is non-renewable, and is good for preparing and can produce pollution environment, harm body using process
The gas of health.With the attention of Environmental resource problem, exploitation prepares environmentally friendly adhesive becomes very necessary.Form sediment
Powder is the natural macromolecular material of a cheap class, wide material sources, environmental protection, with it is nontoxic, pollution-free the features such as.If
With Starch Fraction or whole macromolecular materials for replacing fossil resources to synthesize, wood adhesive is applied to, it will to adhesive
Industry and starch industry play great facilitation.Therefore, in recent years, starch adhesive is friendly as a class green environment
Type adhesive is constantly of interest by numerous scholars.Inventor is in a kind of patent " system of cold curing tapioca gluing agent
Further esterification modification tapioca, is entered using hot setting method on the basis of Preparation Method, application number 2016107690967 "
Row solidification, improves and improves the various aspects of performance of esterification modification starch adhesive, there is provided a kind of excellent performance, response time is short,
It is simple to operate, be suitable for hot setting type esterification modification starch adhesive of industrial applications and preparation method thereof.
The content of the invention
In order to overcome water resistance that is of the prior art not enough and being effectively improved plywood, the invention provides a kind of anti-
It is short, simple to operate between seasonable, be suitable for hot setting type esterification modification starch adhesive of industrial applications and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
A kind of hot setting type esterification modification Cassava starch adhesive, described hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent
Make, its parts by weight be respectively 80～100 parts Modified Oxidize Starth Adhesive stick, 7～12 parts of isocyanates, 0.5～1.5
The antioxidant, 0.5～2 part of fire retardant, 0.02～0.2 part of light stabilizer, 0.5～1 part of UV absorbent of part, wherein
The composition of Modified Oxidize Starth Adhesive stick includes tapioca, polyvinyl alcohol, sodium lauryl sulphate, dodecenylsuccinic acid
Acid anhydride.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described Modified Oxidize Starth Adhesive stick
The parts by weight of middle tapioca are 100 parts, the parts by weight of polyvinyl alcohol are 8 parts, the parts by weight of sodium lauryl sulphate
Parts by weight for 2～3 parts, dodecenylsuccinic acid acid anhydride are 4～10 parts.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described tapioca is configured to Maninot esculenta crantz.
Starch emulsion, the concentration of described tapioca emulsion is 35～42wt%.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described polyvinyl alcohol is configured to gather
Glycohol solution, the concentration of described poly-vinyl alcohol solution is 10～15wt%.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described dodecenylsuccinic acid acid anhydride is matched somebody with somebody
Dodecenylsuccinic acid anhydride solution is made, the concentration of described dodecenylsuccinic acid anhydride solution is 17%～27wt%.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described antioxidant includes the uncles of 2,6- bis-
The quality of butyl -4- cresol and the double lauryls of thio-2 acid, BHT and the double lauryls of thio-2 acid
Than being 2:1.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described fire retardant is BDP (bis-phenol-a
Double (diphenyl phosphates)).
Hot setting type esterification modification Cassava starch adhesive of the present invention, described light stabilizer is 4- benzoyls
Epoxide -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described UV absorbent is 2- hydroxyls
Base -4- oxy-octyl benzophenones.
The preparation method of hot setting type esterification modification Cassava starch adhesive of the present invention, comprises the steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, in load weighted tapioca weight portion is added
Number is 138～186 parts of distilled water, and being placed on magnetic force heating stirrer carries out heated and stirred, 40 DEG C of heating-up temperature, during stirring
Between 10～30min, 200～500rad/min of speed of agitator, obtain tapioca emulsion, maintain the temperature at 40 DEG C, it is stand-by；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reactor with agitator, to weighing
Polyvinyl alcohol in add parts by weight to be 46～72 parts of distilled water, 90 DEG C are warming up under conditions of stirring, mixing time 5
～10min, 200～500rad/min of speed of agitator, after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, stand-by；
Step 3, the tapioca emulsion for preparing step 1 are added in the poly-vinyl alcohol solution that step 2 is prepared, in temperature
Under conditions of 40 DEG C, 200～500rad/min of speed of agitator, Deca concentration is for NaOH solution regulation system pH of 10wt%
8, retention time 30min, obtain tapioca mixed liquor；
Step 4, the sodium lauryl sulphate for weighing 2～3 parts respectively according to parts by weight, 4～10 parts of laurylene base fourth
Dicarboxylic anhydride, adds the distilled water that parts by weight are 18～29 parts to be configured to laurylene in load weighted dodecenylsuccinic acid acid anhydride
Base succinic anhydride solution, load weighted sodium lauryl sulphate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force
It is stirred on heating stirrer, 30～60min of mixing time, 200～500rad/min of speed of agitator makes pre-emulsification molten
Liquid, it is stand-by；
Step 5, the pre-emulsification solution for preparing step 4 under conditions of heated and stirred are slowly dropped to step 3 and prepare
Tapioca mixed liquor in, heating-up temperature is 55 DEG C, 100～200rad/min of speed of agitator, and Deca concentration is for 10wt%
NaOH solution regulation system pH be 9 after, stand 50min, obtain esterification modification Cassava starch adhesive；
Step 6, the isocyanates that 7～12 parts are weighed according to parts by weight, 0.5～1.5 part of antioxidant, 0.5～2 part
Fire retardant, 0.02～0.2 part of light stabilizer, 0.5～1 part of UV absorbent, 80～100 parts the step of 4 prepare esters
Change Modified Oxidize Starth Adhesive stick, under conditions of stirring by load weighted isocyanates, antioxidant, fire retardant, light stabilizer,
UV absorbent is added in esterification modification Cassava starch adhesive, 100～200rad/min of speed of agitator, and mixing time 20～
60min, obtains hot setting type esterification modification Cassava starch adhesive.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the model of described polyvinyl alcohol
RS-2117, RS-1717, RS-1788 or RS-1799.
Hot setting type esterification modification Cassava starch adhesive of the present invention, described tapioca is due to its side chain
Content of starch is high, and tack is big etc., and characteristic has great advantage in adhesive producing field tool；Using esterification modification tapioca, wood
Alkyl or aromatic hydrocarbyl in esterified dose of activity hydroxy in sweet potato starch molecule on 2,3,6 replaces to form starch derivatives
Biology, due to introducing long-chain molecule, its water resistance is obviously improved.Conventional esterifying agent includes various anhydride, laurylene
Base succinic anhydride (DDSA) strand is longer, has excellent hydrophobic property as esterifying agent.Esterification modification starch adhesive
Preparation technology includes two methods of wet method and dry method, and wet processing is contacted with esterifying agent compared to dry process starch granuless and more filled
Point, the extent of reaction is higher, and it is also higher that it prepares product property, therefore the present invention adopts wet processing.In addition, DDSA is in water
Dissolubility is relatively low, and not exclusively, esterifying agent is first carried out pre-emulsification to the reaction with starch by the present invention, is then mixed with starch milk again
Conjunction is reacted.PVA can wrap starch granuless as protecting colloid, play a part of thickening.Carbimide. is added during applying glue
Used as cross-linking agent, isocyanates contain unsaturated group to ester, and reactivity is high, can be with starch and sheet material under high temperature and pressure
In active group there is violent reaction, form firm chemical bond, improve bonding strength.Esterification tapioca course of reaction
Chemical equation it is as follows：
Antioxidant of the present invention includes the double lauryls of BHT and thio-2 acid, 2,6- di-t-butyls-
4- cresol is in the oil industry various lubricating oil, the excellent antioxidant of secondary processing of gasoline, paraffin and some other mineral oil,
The double lauryls of thio-2 acid have the effect of peroxynitrite decomposition compound.Can be used as polyethylene, polypropylene, ABS resin, polrvinyl chloride
Deng auxiliary antioxidant, have do not pollute, not colored, high temperature process when Undec feature；2,6- di-t-butyl -4- cresol and sulfur
For the double lauryl antioxidant synergism of dipropionic acid, is used aborning the antioxygenic property that both can improve, and can reduce
Toxicity and cost.Bis-phenol-a of the present invention double (diphenyl phosphates) is Halogen, low cigarette, the environment friendly flame retardant of bottom poison.Light of the present invention
Stabilizer 4- benzoyloxy -2,2,6,6- tetramethyl piperidines and UV absorbent Octabenzone
Synergy, shielding or absorb ultraviolet energy, quenching singlet oxygen and by hydroperoxide decomposition into inert matter etc.
Function, makes high molecular polymer under the radiation of light, can exclude or slow down photochemical reaction probability, prevents or postpone photoaging
Process, so as to reach extend polymer service life.
The inventive method process is simple, takes short, low cost, and the function admirable of prepared starch adhesive.Using this
Method can effectively improve the bonding strength and water resistance of starch adhesive.
Cassava starch adhesive modest viscosity obtained by the present invention, stable storing, layering is slow；Obtained Maninot esculenta crantz. of the invention
Starch adhesive preparation process is simple is easy to operate, takes short；Obtained Cassava starch adhesive water resistance of the invention is excellent, glue
Close excellent strength；Present invention preparation reaction temperature is low, and postprocessing working procedures are simple, greatly reduce esterification modification tapioca gluing
The producting process difficulty of agent, it is easy to accomplish industrialized production.
Description of the drawings
Fig. 1 is sheet test specimen sawing shape and size front view prepared by the present invention；
Fig. 2 is sheet test specimen sawing shape and size top view prepared by the present invention.
Specific embodiment
Specific embodiment one：
A kind of hot setting type esterification modification Cassava starch adhesive, described hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent
Make, its parts by weight be respectively 80 parts Modified Oxidize Starth Adhesive stick, 8 parts of isocyanates, 0.5 part of antioxidant, 0.5
The fire retardant, 0.02 part of light stabilizer, 0.5 part of UV absorbent of part, the wherein composition of Modified Oxidize Starth Adhesive stick
Including tapioca, polyvinyl alcohol, sodium lauryl sulphate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described Modified Oxidize Starth Adhesive
In stick the parts by weight of tapioca be the parts by weight of 100, polyvinyl alcohol be 8 parts, the weight portion of sodium lauryl sulphate
Number is 2 parts, the parts by weight of dodecenylsuccinic acid acid anhydride are 4 parts.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described tapioca is configured to
Tapioca emulsion, the concentration of described tapioca emulsion is 39wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described polyvinyl alcohol is with preparation
Into poly-vinyl alcohol solution, the concentration of described poly-vinyl alcohol solution is 15wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, and the concentration of described dodecenylsuccinic acid anhydride solution is 17wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described antioxidant includes 2,6-
Di-t-butyl -4- cresol and the double lauryls of thio-2 acid, BHT and the double lauryls of thio-2 acid
Mass ratio is 2:1.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described UV absorbent is
Octabenzone.
Specific embodiment two：
The preparation method of the hot setting type esterification modification Cassava starch adhesive according to specific embodiment one, bag
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, in load weighted tapioca weight portion is added
Number is 156 parts of distilled water, and being placed on magnetic force heating stirrer carries out heated and stirred, 40 DEG C of heating-up temperature, mixing time
10min, speed of agitator 200rad/min, obtain tapioca emulsion, maintain the temperature at 40 DEG C, stand-by；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reactor with agitator, to weighing
Polyvinyl alcohol in add parts by weight to be 46 parts of distilled water, be warming up to 90 DEG C under conditions of stirring, mixing time 5min,
Speed of agitator 200rad/min, after polyvinyl alcohol is completely dissolved, is cooled to 40 DEG C, stand-by；
Step 3, the tapioca emulsion for preparing step 1, in being added to the poly-vinyl alcohol solution of step 2 preparation, in temperature
Spend under conditions of 40 DEG C, speed of agitator 200rad/min, Deca concentration is 8 for NaOH solution regulation system pH of 10wt%,
Retention time 30min, obtains tapioca mixed liquor；
Step 4, the sodium lauryl sulphate for weighing 2 parts respectively according to parts by weight, 4 parts of dodecenylsuccinic acid acid anhydride,
The distilled water that parts by weight are 21 parts is added to be configured to dodecenylsuccinic acid acid anhydride in load weighted dodecenylsuccinic acid acid anhydride
Solution, load weighted sodium lauryl sulphate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force heating stirrer
On be stirred, mixing time 30min, speed of agitator 200rad/min makes pre-emulsification solution, stand-by；
Step 5, the pre-emulsification solution for preparing step 4 under conditions of heated and stirred are slowly dropped to step 3 and prepare
Tapioca mixed liquor in, heating-up temperature be 55 DEG C, speed of agitator 100rad/min, Deca concentration for 10wt% NaOH it is molten
Liquid regulation system pH be 9 after, stand 50min, obtain esterification modification Cassava starch adhesive；
Step 6, the isocyanates that 8 parts are weighed according to parts by weight, 0.5 part of antioxidant, 0.5 part of fire retardant, 0.02
Part light stabilizer, 0.5 part of UV absorbent, 80 parts the step of 4 prepare esterification modification Cassava starch adhesives, stirring
Load weighted isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent are added into esterification modification under conditions of mixing
In Cassava starch adhesive, speed of agitator 200rad/min, mixing time 60min obtains hot setting type esterification modification Maninot esculenta crantz.
Starch adhesive.
Specific embodiment three：
A kind of hot setting type esterification modification Cassava starch adhesive, described hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent
Make, its parts by weight be respectively 100 parts Modified Oxidize Starth Adhesive stick, 12 parts of isocyanates, 1.5 parts of antioxidant, 2
The fire retardant, 0.2 part of light stabilizer, 1 part of UV absorbent of part, the composition of wherein Modified Oxidize Starth Adhesive stick includes
Tapioca, polyvinyl alcohol, sodium lauryl sulphate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described Modified Oxidize Starth Adhesive
In stick the parts by weight of tapioca be the parts by weight of 100, polyvinyl alcohol be 8 parts, the weight portion of sodium lauryl sulphate
Number is 3 parts, the parts by weight of dodecenylsuccinic acid acid anhydride are 10 parts.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described tapioca is configured to
Tapioca emulsion, the concentration of described tapioca emulsion is 35wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described polyvinyl alcohol is with preparation
Into poly-vinyl alcohol solution, the concentration of described poly-vinyl alcohol solution is 10wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, and the concentration of described dodecenylsuccinic acid anhydride solution is 27wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described antioxidant includes 2,6-
Di-t-butyl -4- cresol and the double lauryls of thio-2 acid, BHT and the double lauryls of thio-2 acid
Mass ratio is 2:1.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described UV absorbent is
Octabenzone.
Specific embodiment four：
The preparation method of the hot setting type esterification modification Cassava starch adhesive according to specific embodiment three, bag
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, in load weighted tapioca weight portion is added
Number is 185 parts of distilled water, and being placed on magnetic force heating stirrer carries out heated and stirred, 40 DEG C of heating-up temperature, mixing time
15min, speed of agitator 500rad/min, obtain tapioca emulsion, maintain the temperature at 40 DEG C, stand-by；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reactor with agitator, to weighing
Polyvinyl alcohol in add parts by weight to be 72 parts of distilled water, 90 DEG C are warming up under conditions of stirring, mixing time
10min, speed of agitator 500rad/min, after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, stand-by；
Step 3, the tapioca emulsion for preparing step 1, in being added to the poly-vinyl alcohol solution of step 2 preparation, in temperature
Spend under conditions of 40 DEG C, speed of agitator 200rad/min, Deca concentration is 8 for NaOH solution regulation system pH of 10wt%,
Retention time 30min, obtains tapioca mixed liquor；
Step 4, the sodium lauryl sulphate for weighing 3 parts respectively according to parts by weight, 10 parts of dodecenylsuccinic acid acid anhydride,
The distilled water that parts by weight are 27 parts is added to be configured to 27wt% laurylene base fourths in load weighted dodecenylsuccinic acid acid anhydride
Diacid anhydride solution, load weighted sodium lauryl sulphate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force heating
It is stirred on agitator, mixing time 60min, speed of agitator 200rad/min, makes pre-emulsification solution, it is stand-by；
Step 5, the pre-emulsification solution for preparing step 4 under conditions of heated and stirred are slowly dropped to step 3 and prepare
Tapioca mixed liquor in, heating-up temperature be 55 DEG C, speed of agitator 200rad/min, Deca concentration for 10wt% NaOH it is molten
Liquid regulation system pH be 10 after, stand 50min, obtain esterification modification Cassava starch adhesive；
Step 6, the isocyanates that 12 parts are weighed according to parts by weight, 1.5 parts of antioxidant, 2 parts of fire retardant, 0.2 part
Light stabilizer, 1 part of UV absorbent, 100 parts the step of 4 prepare esterification modification Cassava starch adhesives, stirring
Under conditions of by load weighted isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent add esterification modification wood
In sweet potato starch adhesive, 100～200rad/min of speed of agitator, 20～60min of mixing time obtain the esterification of hot setting type and change
Property Cassava starch adhesive.
Specific embodiment five：
A kind of hot setting type esterification modification Cassava starch adhesive, described hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent
Make, its parts by weight be respectively 90 parts Modified Oxidize Starth Adhesive stick, 9 parts of isocyanates, 1.5 parts of antioxidant, 2 parts
Fire retardant, 0.2 part of light stabilizer, 1 part of UV absorbent, wherein the composition of Modified Oxidize Starth Adhesive stick include wood
Sweet potato starch, polyvinyl alcohol, sodium lauryl sulphate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described Modified Oxidize Starth Adhesive
In stick the parts by weight of tapioca be the parts by weight of 100, polyvinyl alcohol be 8 parts, the weight portion of sodium lauryl sulphate
Number is 2.5 parts, the parts by weight of dodecenylsuccinic acid acid anhydride are 6 parts.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described tapioca is configured to
Tapioca emulsion, the concentration of described tapioca emulsion is 42wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described polyvinyl alcohol is with preparation
Into poly-vinyl alcohol solution, the concentration of described poly-vinyl alcohol solution is 12wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, and the concentration of described dodecenylsuccinic acid anhydride solution is 21wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described antioxidant includes 2,6-
Di-t-butyl -4- cresol and the double lauryls of thio-2 acid, BHT and the double lauryls of thio-2 acid
Mass ratio is 2:1.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described UV absorbent is
Octabenzone.
Instantiation six：
The preparation method of the hot setting type esterification modification Cassava starch adhesive according to specific embodiment five, bag
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, in load weighted tapioca weight portion is added
Number is 138 parts of distilled water, and being placed on magnetic force heating stirrer carries out heated and stirred, 40 DEG C of heating-up temperature, mixing time
15min, speed of agitator 500rad/min, obtain tapioca emulsion, maintain the temperature at 40 DEG C, stand-by；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reactor with agitator, to weighing
Polyvinyl alcohol in add parts by weight to be 58.5 parts of distilled water, 90 DEG C are warming up under conditions of stirring, mixing time
10min, speed of agitator 500rad/min, after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, stand-by；
Step 3, the tapioca emulsion for preparing step 1, in being added to the poly-vinyl alcohol solution of step 2 preparation, in temperature
Spend under conditions of 40 DEG C, speed of agitator 200rad/min, Deca concentration is 8 for NaOH solution regulation system pH of 10wt%,
Retention time 30min, obtains tapioca mixed liquor；
Step 4, the sodium lauryl sulphate for weighing 2.5 parts respectively according to parts by weight, 6 parts of dodecenylsuccinic acid
Acid anhydride, adds the distilled water that parts by weight are 29 parts to be configured to 21wt% laurylene bases in load weighted dodecenylsuccinic acid acid anhydride
Succinic anhydride solution, load weighted sodium lauryl sulphate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force and is added
It is stirred on thermal agitation device, mixing time 60min, speed of agitator 200rad/min, makes pre-emulsification solution, it is stand-by；
Step 5, the pre-emulsification solution for preparing step 4 under conditions of heated and stirred are slowly dropped to step 3 and prepare
Tapioca mixed liquor in, heating-up temperature be 55 DEG C, speed of agitator 200rad/min, Deca concentration for 10wt% NaOH it is molten
Liquid regulation system pH be 8 after, stand 50min, obtain esterification modification Cassava starch adhesive；
Step 6, the isocyanates that 9 parts are weighed according to parts by weight, 1.5 parts of antioxidant, 2 parts of fire retardant, 0.2 part
Light stabilizer, 1 part of UV absorbent, 90 parts the step of 4 prepare esterification modification Cassava starch adhesives, stirring bar
Load weighted isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent are added into esterification modification para arrowroot under part
In arogel stick, 100～200rad/min of speed of agitator, 20～60min of mixing time obtain hot setting type esterification modification wood
Sweet potato starch adhesive.
Specific embodiment seven：
A kind of hot setting type esterification modification Cassava starch adhesive, described hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent
Make, its parts by weight be respectively 90 parts Modified Oxidize Starth Adhesive stick, 7 parts of isocyanates, 1.5 parts of antioxidant, 2 parts
Fire retardant, 0.2 part of light stabilizer, 1 part of UV absorbent, wherein the composition of Modified Oxidize Starth Adhesive stick include wood
Sweet potato starch, polyvinyl alcohol, sodium lauryl sulphate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described Modified Oxidize Starth Adhesive
In stick the parts by weight of tapioca be the parts by weight of 100, polyvinyl alcohol be 8 parts, the weight portion of sodium lauryl sulphate
Number is 2 parts, the parts by weight of dodecenylsuccinic acid acid anhydride are 6 parts.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described tapioca is configured to
Tapioca emulsion, the concentration of described tapioca emulsion is 35wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described polyvinyl alcohol is with preparation
Into poly-vinyl alcohol solution, the concentration of described poly-vinyl alcohol solution is 12wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, and the concentration of described dodecenylsuccinic acid anhydride solution is 27wt%.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described antioxidant includes 2,6-
Di-t-butyl -4- cresol and the double lauryls of thio-2 acid, BHT and the double lauryls of thio-2 acid
Mass ratio is 2:1.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, described UV absorbent is
Octabenzone.
Specific embodiment eight：
The preparation method of the hot setting type esterification modification Cassava starch adhesive according to specific embodiment seven, bag
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, in load weighted tapioca weight portion is added
Number is 156 parts of distilled water, and being placed on magnetic force heating stirrer carries out heated and stirred, 40 DEG C of heating-up temperature, mixing time
15min, speed of agitator 500rad/min, obtain tapioca emulsion, maintain the temperature at 40 DEG C, stand-by；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reactor with agitator, to weighing
Polyvinyl alcohol in add parts by weight to be 53 parts of distilled water, 90 DEG C are warming up under conditions of stirring, mixing time
10min, speed of agitator 500rad/min, after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, stand-by；
Step 3, the tapioca emulsion for preparing step 1, in being added to the poly-vinyl alcohol solution of step 2 preparation, in temperature
Spend under conditions of 40 DEG C, speed of agitator 200rad/min, Deca concentration is 8 for NaOH solution regulation system pH of 10wt%,
Retention time 30min, obtains tapioca mixed liquor；
Step 4, the sodium lauryl sulphate for weighing 2 parts respectively according to parts by weight, 6 parts of dodecenylsuccinic acid acid anhydride,
The distilled water that parts by weight are 18 parts is added to be configured to 25wt% laurylene base fourths in load weighted dodecenylsuccinic acid acid anhydride
Diacid anhydride solution, load weighted sodium lauryl sulphate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force heating
It is stirred on agitator, mixing time 60min, speed of agitator 200rad/min, makes pre-emulsification solution, it is stand-by；
Step 5, the pre-emulsification solution for preparing step 4 under conditions of heated and stirred are slowly dropped to step 3 and prepare
Tapioca mixed liquor in, heating-up temperature be 55 DEG C, speed of agitator 200rad/min, Deca concentration for 10wt% NaOH it is molten
Liquid regulation system pH be 9 after, stand 50min, obtain esterification modification Cassava starch adhesive；
Step 6, the isocyanates that 7 parts are weighed according to parts by weight, 1.5 parts of antioxidant, 2 parts of fire retardant, 0.2 part
Light stabilizer, 1 part of UV absorbent, 90 parts the step of 4 prepare esterification modification Cassava starch adhesives, stirring bar
Load weighted isocyanates, antioxidant, fire retardant, light stabilizer, UV absorbent are added into esterification modification para arrowroot under part
In arogel stick, 100～200rad/min of speed of agitator, 20～60min of mixing time obtain hot setting type esterification modification wood
Sweet potato starch adhesive.
Hot setting type esterification modification starch adhesive prepared by specific embodiment one to embodiment eight is applied
Glue suppresses under heat three layers of poplar plywood.120 DEG C of hot pressing temperature, 3～4MPa of pressure, the sheet of preparation places 24h
Afterwards, according to GB/T 17657-2013《Test methods of evaluating the properties of wood-based panels and surface decorated wood-based panels》Saw system is carried out to plywood.Examination
Part size 100 ± 1mm of length, wide 25 ± 1mm, shear plane 25mm, concrete sawing shape and size are as shown in accompanying drawing 1, accompanying drawing 2.
By the physico-chemical property of hot setting type esterification modification starch adhesive prepared by specific embodiment two, four, six, eight
And mechanics properties testing result is in table 1 below.
The performance test of the hot setting type esterification modification Cassava starch adhesive of table 1
In testing above, the test of prepared esterification Cassava starch adhesive viscosity and solids content is with reference to GBT-
14074-2006《Wood adhesive and its resin method of inspection》, wet shape bonding strength is with reference to GB/T 17657-2013《Plywood
Strength detection》, 3h will be soaked in the water of plywood immersion (63 ± 3) DEG C of the adhesive compacting in table 1, the test examination under hygrometric state
Part stretches bonding strength.
The wet shape bonding strength of gained is satisfied by II class Strength of Plywood (>=0.7MPa) of GBT 9846-2015 countries in table,
So the esterification modification starch adhesive prepared by the present invention, bonding strength is completely up to standard, function admirable.
Claims (10)
1. a kind of hot setting type esterification modification Cassava starch adhesive, it is characterised in that：Described hot setting type esterification changes
Property Cassava starch adhesive be mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, purple
Ultraviolet absorbers are made, and its parts by weight is respectively 80～100 parts of Modified Oxidize Starth Adhesive stick, 7～12 parts of Carbimide.
Ester, 0.5～1.5 part of antioxidant, 0.5～2 part of fire retardant, 0.02～0.2 part of light stabilizer, 0.5～1 part of ultraviolet
Absorbent, the wherein composition of Modified Oxidize Starth Adhesive stick include tapioca, polyvinyl alcohol, sodium lauryl sulphate, 12
Enetutanedioic acid anhydride.
2. hot setting type esterification modification Cassava starch adhesive according to claim 1, it is characterised in that：Described changes
Property Cassava starch adhesive in tapioca parts by weight be 70～100, polyvinyl alcohol parts by weight be 5.6～8 parts, ten
The parts by weight of sodium dialkyl sulfate are 2～3 parts, the parts by weight of dodecenylsuccinic acid acid anhydride are 4～10 parts, starch esterification pH
For 8～10.
3. hot setting type esterification modification Cassava starch adhesive according to claim 1 and 2, it is characterised in that：It is described
Tapioca be configured to tapioca emulsion, the concentration of described tapioca emulsion is 35～42wt%.
4. hot setting type esterification modification Cassava starch adhesive according to claim 1 and 2, it is characterised in that：It is described
Polyvinyl alcohol be configured to poly-vinyl alcohol solution, the concentration of described poly-vinyl alcohol solution is 10～15wt%.
5. hot setting type esterification modification Cassava starch adhesive according to claim 1 and 2, it is characterised in that：It is described
Dodecenylsuccinic acid acid anhydride be configured to dodecenylsuccinic acid anhydride solution, the concentration of described dodecenylsuccinic acid anhydride solution
For 17～27wt%.
6. hot setting type esterification modification Cassava starch adhesive according to claim 1 and 2, it is characterised in that：It is described
Antioxidant include the double lauryls of BHT and thio-2 acid, BHT and thio
The mass ratio of the double lauryls of dipropionic acid is 2:1.
7. hot setting type esterification modification Cassava starch adhesive according to claim 1 and 2, it is characterised in that：It is described
Fire retardant be BDP.
8. hot setting type esterification modification Cassava starch adhesive according to claim 1 and 2, it is characterised in that：It is described
Light stabilizer be 4- benzoyloxy -2,2,6,6- tetramethyl piperidines.
9. hot setting type esterification modification Cassava starch adhesive according to claim 1 and 2, it is characterised in that：It is described
UV absorbent be Octabenzone.
10. the preparation method of the hot setting type esterification modification Cassava starch adhesive described in a kind of one of claim 1-9, its
It is characterised by：Comprise the steps：
Step 1, the tapioca that 70～100 parts are weighed according to parts by weight, in load weighted tapioca weight portion is added
Number is 138～186 parts of distilled water, and being placed on magnetic force heating stirrer carries out heated and stirred, 40 DEG C of heating-up temperature, during stirring
Between 10～30min, 200～500rad/min of speed of agitator, obtain tapioca emulsion, maintain the temperature at 40 DEG C, it is stand-by；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reactor with agitator, to load weighted poly-
Add parts by weight to be 46～72 parts of distilled water in vinyl alcohol, be warming up to 90 DEG C under conditions of stirring, mixing time 5～
10min, 200～500rad/min of speed of agitator, after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, stand-by；
Step 3, the tapioca emulsion for preparing step 1, in being added to the poly-vinyl alcohol solution of step 2 preparation, be in temperature
40 DEG C, under conditions of 200～500rad/min of speed of agitator, Deca concentration is 8 for NaOH solution regulation system pH of 10wt%,
Retention time 30min, obtains tapioca mixed liquor；
Step 4, the sodium lauryl sulphate for weighing 2～3 parts respectively according to parts by weight, 4～10 parts of dodecenylsuccinic acid
Acid anhydride, adds the distilled water that parts by weight are 18～29 parts to be configured to laurylene base fourth in load weighted dodecenylsuccinic acid acid anhydride
Diacid anhydride solution, load weighted sodium lauryl sulphate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force heating
It is stirred on agitator, 30～60min of mixing time, 200～500rad/min of speed of agitator makes pre-emulsification solution, treats
With；
Step 5, the pre-emulsification solution for preparing step 4 under conditions of heated and stirred are slowly dropped to wood prepared by step 3
In sweet potato starch mixed liquor, heating-up temperature is 55 DEG C, 100～200rad/min of speed of agitator, and Deca concentration is the NaOH of 10wt%
Solution regulation system pH=8,9,10,50min is stood, obtain esterification modification Cassava starch adhesive；
Step 6, the isocyanates that 7～12 parts are weighed according to parts by weight, 0.5～1.5 part of antioxidant, 0.5～2 part fire-retardant
Agent, 0.02～0.2 part of light stabilizer, 0.5～1 part of UV absorbent, 80～100 parts the step of 4 prepare esterifications change
Property Cassava starch adhesive, by load weighted isocyanates, antioxidant, fire retardant, light stabilizer, ultraviolet under conditions of stirring
Light absorbers are added in esterification modification Cassava starch adhesive, 100～200rad/min of speed of agitator, and mixing time 20～
60min, obtains hot setting type esterification modification Cassava starch adhesive.
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| CN113683982A (en) * | 2021-09-11 | 2021-11-23 | 杭州永晶科技有限公司 | Glue for compounding corrugated paper and preparation method thereof |
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