CN106590468B - Hot setting type esterification modification Cassava starch adhesive and preparation method thereof - Google Patents
Hot setting type esterification modification Cassava starch adhesive and preparation method thereof Download PDFInfo
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- CN106590468B CN106590468B CN201710094349.XA CN201710094349A CN106590468B CN 106590468 B CN106590468 B CN 106590468B CN 201710094349 A CN201710094349 A CN 201710094349A CN 106590468 B CN106590468 B CN 106590468B
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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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- Adhesives Or Adhesive Processes (AREA)
Abstract
Hot setting type esterification modification Cassava starch adhesive and preparation method thereof, it belongs to adhesive preparing technical field.The raw material of the adhesive generally used in timber industry at present is non-renewable.The present invention is mainly made of Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber, its parts by weight is respectively 80~100 parts of Modified Oxidize Starth Adhesive stick, 7~12 parts of isocyanates, 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 ultra-violet absorber, and the ingredient of wherein Modified Oxidize Starth Adhesive stick includes tapioca, polyvinyl alcohol, lauryl sodium sulfate, dodecenylsuccinic acid acid anhydride.Modest viscosity of the present invention, stable storing, layering is slow, and preparation process is simple to operation, takes short；Water resistance is excellent, and bonding strength is excellent, it is easy to accomplish industrialized production.
Description
Technical field
The invention belongs to adhesive preparing technical fields, and in particular to a kind of hot setting type esterification modification Tapioca adhesive
Stick and preparation method thereof.
Background technology
The adhesive generally used in timber industry at present is the conjunction prepared by ureaformaldehyde, phenolic aldehyde, melamine resin
At macromolecule adhesive, raw material is non-renewable, and is preparing and will produce that pollution environment, to endanger body strong using process
The gas of health.With the attention of Environmental resource problem, exploitation, which prepares environmentally friendly adhesive, becomes very necessary.It forms sediment
Powder is that one kind is cheap, derives from a wealth of sources, environmentally protective natural macromolecular material, is had the characteristics that nontoxic, pollution-free.If
With Starch Fraction or the high molecular material of whole substitution fossil resources synthesis, it is applied to wood adhesive, it will to adhesive
Industry and starch industry play great facilitation.Therefore, in recent years, starch adhesive is friendly as a kind of green environment
Type adhesive is constantly of interest by numerous scholars.Inventor is in a kind of patent " system of room temperature curing tapioca gluing agent
Further esterification modification tapioca on the basis of Preparation Method, application number 2016107690967 ", using hot setting method into
Row solidification, improve and improve the various aspects of performance of esterification modification starch adhesive, provide one kind is had excellent performance, the reaction time is short,
Hot setting type esterification modification starch adhesive and preparation method thereof easy to operate, to be suitable for industrial applications.
Invention content
In order to overcome water resistance that is in the prior art insufficient and being effectively improved glued board, the present invention provides a kind of anti-
Hot setting type esterification modification starch adhesive and preparation method thereof short, easy to operate between seasonable, to be suitable for industrial applications.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of hot setting type esterification modification Cassava starch adhesive, the hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber
It is made, parts by weight are respectively 80~100 parts of 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 ultra-violet absorber of part, wherein
The ingredient of Modified Oxidize Starth Adhesive stick includes tapioca, polyvinyl alcohol, lauryl sodium sulfate, dodecenylsuccinic acid
Acid anhydride.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the 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 lauryl sodium sulfate
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, the tapioca are configured to cassava
Starch emulsion, a concentration of 35~42wt% of the tapioca lotion.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the polyvinyl alcohol are configured to gather
Glycohol solution, a concentration of 10~15wt% of the poly-vinyl alcohol solution.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the dodecenylsuccinic acid acid anhydride are matched
Dodecenylsuccinic acid anhydride solution, a concentration of 17%~27wt% of the dodecenylsuccinic acid anhydride solution is made.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the antioxidant include 2,6-, bis- uncles
Butyl -4- cresols and the double lauryls of thio-2 acid, the quality of 2,6-di-tert-butyl-4-methylphenol and the double lauryls of thio-2 acid
Than being 2:1.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the fire retardant are BDP (bis-phenol-a
Bis- (diphenyl phosphates)).
Hot setting type esterification modification Cassava starch adhesive of the present invention, the light stabilizer are 4- benzoyls
Oxygroup -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the ultra-violet absorber are 2- hydroxyls
Base -4- oxy-octyl benzophenones.
The preparation method of hot setting type esterification modification Cassava starch adhesive of the present invention, includes the following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, parts by weight are added into load weighted tapioca
Number is 138~186 parts of distilled water, is placed on magnetic force heating stirrer and carries out heating stirring, 40 DEG C of heating temperature, when stirring
Between 10~30min, 200~500rad/min of speed of agitator obtains tapioca lotion, maintains the temperature at 40 DEG C, for use；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reaction kettle with blender, to weighing
Polyvinyl alcohol in parts by weight are added is 46~72 parts of distilled water, be warming up to 90 DEG C under stirring conditions, mixing time 5
~10min, 200~500rad/min of speed of agitator after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, for use；
Tapioca lotion prepared by step 1 is added in the poly-vinyl alcohol solution that step 2 is prepared by step 3, in temperature
Under conditions of 40 DEG C, 200~500rad/min of speed of agitator, the NaOH solution regulation system pH that a concentration of 10wt% is added dropwise is
8, retention time 30min obtain tapioca mixed liquor；
Step 4, the lauryl sodium sulfate for weighing 2~3 parts respectively according to parts by weight, 4~10 parts of laurylene base fourth
The distilled water that parts by weight are 18~29 parts is added into load weighted dodecenylsuccinic acid acid anhydride and is configured to laurylene for dicarboxylic anhydride
Load weighted lauryl sodium sulfate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force by base succinic anhydride solution
It is stirred on heating stirrer, 30~60min of mixing time, it is molten that pre-emulsification is made in 200~500rad/min of speed of agitator
Liquid, for use；
The pre-emulsification solution that step 4 prepares is slowly dropped to step 3 under conditions of heating stirring and prepares by step 5
Tapioca mixed liquor in, heating temperature be 55 DEG C, 100~200rad/min of speed of agitator is added dropwise a concentration of 10wt%'s
After NaOH solution regulation system pH is 9,50min is stood, esterification modification Cassava starch adhesive is obtained；
Step 6, weighed according to parts by weight 7~12 parts of isocyanates, 0.5~1.5 part of antioxidant, 0.5~2 part
Ester prepared by fire retardant, 0.02~0.2 part of light stabilizer, 0.5~1 part of ultra-violet absorber, 80~100 parts of step 4
Change Modified Oxidize Starth Adhesive stick, under stirring conditions by load weighted isocyanates, antioxidant, fire retardant, light stabilizer,
Ultra-violet absorber 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 the polyvinyl alcohol
RS-2117, RS-1717, RS-1788 or RS-1799.
Hot setting type esterification modification Cassava starch adhesive of the present invention, the tapioca is due to its branch
The characteristics such as content of starch is high, and tack is big have great advantage in adhesive producing field tool；Utilize esterification modification tapioca, wood
The alkyl or aromatic hydrocarbyl that activity hydroxy 2 in sweet potato starch molecule, on 3,6 is esterified in agent replace to form starch derivatives
Biology, due to introducing long-chain molecule, water resistance is obviously improved.Common esterifying agent includes various acid anhydrides, laurylene
Base succinic anhydride (DDSA) strand is longer, has excellent hydrophobic property as esterifying agent.Esterification modification starch adhesive
Preparation process includes two methods of wet method and dry method, and wet processing, which is contacted compared to dry process starch granules with esterifying agent, more to be filled
Point, extent of reaction higher, it is also higher to prepare product property, therefore the present invention uses wet processing.In addition, DDSA is in water
Solubility is relatively low, incomplete with reacting for starch, and esterifying agent is first carried out pre-emulsification by the present invention, is then mixed again with starch milk
Conjunction is reacted.PVA can wrap starch granules, play the role of thickening as protecting colloid.Isocyanic acid is added when sizing
Ester is as crosslinking agent, and isocyanates contains unsaturated group, and reactivity is high, can be with starch and plank under high temperature and pressure
In active group violent reaction occurs, form firm chemical bond, improve bonding strength.It is esterified tapioca reaction process
Chemical equation it is as follows：
Antioxidant of the present invention includes 2,6-di-tert-butyl-4-methylphenol and the double lauryls of thio-2 acid, 2,6- di-t-butyls-
4- cresols is various lubricating oil in the oil industry, secondary processing of gasoline, paraffin and some other mineral oil excellent antioxidant,
The double lauryls of thio-2 acid have the function of peroxynitrite decomposition compound.It can be used as polyethylene, polypropylene, ABS resin, polyvinyl chloride
Deng auxiliary antioxidant, have do not pollute, be not colored, high temperature process when Undec feature；2,6- di-t-butyl -4- cresols and sulphur
For the double lauryl antioxidant synergistic effects of dipropionic acid, it is used antioxygenic property not only can be improved in production, but also can reduce
Toxicity and cost.Bis-phenol-a of the present invention bis- (diphenyl phosphates) is the environment friendly flame retardant of Halogen, low cigarette, bottom poison.Light of the present invention
Stabilizer 4- benzoyloxys -2,2,6,6- tetramethyl piperidines and ultra-violet absorber 2-hydroxy-4-n-octoxybenzophenone
Hydroperoxides and are resolved into inert matter etc. at quenching singlet oxygen by synergy, shielding or the energy for absorbing ultraviolet light
Function makes high molecular polymer under the radiation of light, can exclude or slow down photochemical reaction possibility, prevents or postpone light aging
Process, to reach extend polymer service life.
The method of the present invention is simple for process, time-consuming short, at 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 are slow；Cassava produced by the present invention
Starch adhesive preparation process is simple to operation, takes short；Cassava starch adhesive water resistance produced by the present 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 vertical view prepared by the present invention.
Specific implementation mode
Specific implementation mode one：
A kind of hot setting type esterification modification Cassava starch adhesive, the hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber
It is made, parts by weight are respectively 80 parts of Modified Oxidize Starth Adhesive stick, 8 parts of isocyanates, 0.5 part of antioxidant, 0.5
Fire retardant, 0.02 part of light stabilizer, 0.5 part of the ultra-violet absorber, the wherein ingredient of Modified Oxidize Starth Adhesive stick of part
Including tapioca, polyvinyl alcohol, lauryl sodium sulfate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the Modified Oxidize Starth Adhesive
The parts by weight of tapioca are 100 in stick, the parts by weight of polyvinyl alcohol are 8 parts, the parts by weight of lauryl sodium sulfate
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, the tapioca are configured to
Tapioca lotion, a concentration of 39wt% of the tapioca lotion.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the polyvinyl alcohol is with preparation
At poly-vinyl alcohol solution, a concentration of 15wt% of the poly-vinyl alcohol solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, a concentration of 17wt% of the dodecenylsuccinic acid anhydride solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the antioxidant include 2,6-
Di-t-butyl -4- cresols and the double lauryls of thio-2 acid, 2,6-di-tert-butyl-4-methylphenol 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, the fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the ultra-violet absorber are
2-hydroxy-4-n-octoxybenzophenone.
Specific implementation mode two：
The preparation method of hot setting type esterification modification Cassava starch adhesive according to specific implementation mode one, packet
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, parts by weight are added into load weighted tapioca
Number is 156 parts of distilled water, is placed on magnetic force heating stirrer and carries out heating stirring, 40 DEG C of heating temperature, mixing time
10min, speed of agitator 200rad/min obtain tapioca lotion, maintain the temperature at 40 DEG C, for use；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reaction kettle with blender, to weighing
Polyvinyl alcohol in parts by weight are added is 46 parts of distilled water, be warming up to 90 DEG C, mixing time 5min under stirring conditions,
Speed of agitator 200rad/min after polyvinyl alcohol is completely dissolved, is cooled to 40 DEG C, for use；
Step 3, the tapioca lotion for preparing step 1 are added in the poly-vinyl alcohol solution of step 2 preparation, in temperature
Degree is 40 DEG C, under conditions of speed of agitator 200rad/min, and the NaOH solution regulation system pH that a concentration of 10wt% is added dropwise is 8,
Retention time 30min obtains tapioca mixed liquor；
Step 4, the lauryl sodium sulfate 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 into load weighted dodecenylsuccinic acid acid anhydride and is configured to dodecenylsuccinic acid acid anhydride
Load weighted lauryl sodium sulfate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force heating stirrer by solution
On be stirred, pre-emulsification solution is made, for use in mixing time 30min, speed of agitator 200rad/min；
The pre-emulsification solution that step 4 prepares is slowly dropped to step 3 under conditions of heating stirring and prepares by step 5
Tapioca mixed liquor in, heating temperature be 55 DEG C, speed of agitator 100rad/min, the NaOH that a concentration of 10wt% is added dropwise it is molten
After liquid regulation system pH is 9,50min is stood, esterification modification Cassava starch adhesive is obtained；
Step 6 weighs 8 parts of isocyanates, 0.5 part of antioxidant, 0.5 part of fire retardant, 0.02 according to parts by weight
Esterification modification Cassava starch adhesive prepared by the light stabilizer of part, 0.5 part of ultra-violet absorber, 80 parts of step 4, is being stirred
Esterification modification is added in load weighted isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber under conditions of mixing
In Cassava starch adhesive, speed of agitator 200rad/min, mixing time 60min obtain hot setting type esterification modification cassava
Starch adhesive.
Specific implementation mode three：
A kind of hot setting type esterification modification Cassava starch adhesive, the hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber
It is made, parts by weight are respectively 100 parts of 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 ultra-violet absorber of part, the ingredient of wherein Modified Oxidize Starth Adhesive stick include
Tapioca, polyvinyl alcohol, lauryl sodium sulfate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the Modified Oxidize Starth Adhesive
The parts by weight of tapioca are 100 in stick, the parts by weight of polyvinyl alcohol are 8 parts, the parts by weight of lauryl sodium sulfate
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, the tapioca are configured to
Tapioca lotion, a concentration of 35wt% of the tapioca lotion.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the polyvinyl alcohol is with preparation
At poly-vinyl alcohol solution, a concentration of 10wt% of the poly-vinyl alcohol solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, a concentration of 27wt% of the dodecenylsuccinic acid anhydride solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the antioxidant include 2,6-
Di-t-butyl -4- cresols and the double lauryls of thio-2 acid, 2,6-di-tert-butyl-4-methylphenol 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, the fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the ultra-violet absorber are
2-hydroxy-4-n-octoxybenzophenone.
Specific implementation mode four：
The preparation method of hot setting type esterification modification Cassava starch adhesive according to specific implementation mode three, packet
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, parts by weight are added into load weighted tapioca
Number is 185 parts of distilled water, is placed on magnetic force heating stirrer and carries out heating stirring, 40 DEG C of heating temperature, mixing time
15min, speed of agitator 500rad/min obtain tapioca lotion, maintain the temperature at 40 DEG C, for use；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reaction kettle with blender, to weighing
Polyvinyl alcohol in parts by weight are added is 72 parts of distilled water, be warming up to 90 DEG C under stirring conditions, mixing time
10min, speed of agitator 500rad/min after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, for use；
Step 3, the tapioca lotion for preparing step 1 are added in the poly-vinyl alcohol solution of step 2 preparation, in temperature
Degree is 40 DEG C, under conditions of speed of agitator 200rad/min, and the NaOH solution regulation system pH that a concentration of 10wt% is added dropwise is 8,
Retention time 30min obtains tapioca mixed liquor；
Step 4, the lauryl sodium sulfate 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 into load weighted dodecenylsuccinic acid acid anhydride and is configured to 27wt% laurylene base fourths
Load weighted lauryl sodium sulfate is added in dodecenylsuccinic acid anhydride solution diacid anhydride solution, is placed into magnetic force heating
It is stirred on blender, mixing time 60min, pre-emulsification solution is made, for use in speed of agitator 200rad/min；
The pre-emulsification solution that step 4 prepares is slowly dropped to step 3 under conditions of heating stirring and prepares by step 5
Tapioca mixed liquor in, heating temperature be 55 DEG C, speed of agitator 200rad/min, the NaOH that a concentration of 10wt% is added dropwise it is molten
After liquid regulation system pH is 10,50min is stood, esterification modification Cassava starch adhesive is obtained；
Step 6, weighed according to parts by weight 12 parts of isocyanates, 1.5 parts of antioxidant, 2 parts of fire retardant, 0.2 part
Light stabilizer, 1 part of ultra-violet absorber, 100 parts step 4 prepare esterification modification Cassava starch adhesive, stirring
Under conditions of by load weighted isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber be added 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 implementation mode five：
A kind of hot setting type esterification modification Cassava starch adhesive, the hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber
Be made, parts by weight be respectively 90 parts of 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 ultra-violet absorber, wherein the ingredient of Modified Oxidize Starth Adhesive stick include wood
Sweet potato starch, polyvinyl alcohol, lauryl sodium sulfate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the Modified Oxidize Starth Adhesive
The parts by weight of tapioca are 100 in stick, the parts by weight of polyvinyl alcohol are 8 parts, the parts by weight of lauryl sodium sulfate
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, the tapioca are configured to
Tapioca lotion, a concentration of 42wt% of the tapioca lotion.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the polyvinyl alcohol is with preparation
At poly-vinyl alcohol solution, a concentration of 12wt% of the poly-vinyl alcohol solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, a concentration of 21wt% of the dodecenylsuccinic acid anhydride solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the antioxidant include 2,6-
Di-t-butyl -4- cresols and the double lauryls of thio-2 acid, 2,6-di-tert-butyl-4-methylphenol 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, the fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the ultra-violet absorber are
2-hydroxy-4-n-octoxybenzophenone.
Specific example six：
The preparation method of hot setting type esterification modification Cassava starch adhesive according to specific implementation mode five, packet
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, parts by weight are added into load weighted tapioca
Number is 138 parts of distilled water, is placed on magnetic force heating stirrer and carries out heating stirring, 40 DEG C of heating temperature, mixing time
15min, speed of agitator 500rad/min obtain tapioca lotion, maintain the temperature at 40 DEG C, for use；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reaction kettle with blender, to weighing
Polyvinyl alcohol in parts by weight are added is 58.5 parts of distilled water, be warming up to 90 DEG C under stirring conditions, mixing time
10min, speed of agitator 500rad/min after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, for use；
Step 3, the tapioca lotion for preparing step 1 are added in the poly-vinyl alcohol solution of step 2 preparation, in temperature
Degree is 40 DEG C, under conditions of speed of agitator 200rad/min, and the NaOH solution regulation system pH that a concentration of 10wt% is added dropwise is 8,
Retention time 30min obtains tapioca mixed liquor；
Step 4 weighs 2.5 parts of lauryl sodium sulfate, 6 parts of dodecenylsuccinic acid according to parts by weight respectively
The distilled water that parts by weight are 29 parts is added into load weighted dodecenylsuccinic acid acid anhydride and is configured to 21wt% laurylene bases for acid anhydride
Load weighted lauryl sodium sulfate is added in dodecenylsuccinic acid anhydride solution, is placed into magnetic force and adds by succinic anhydride solution
It is stirred on thermal agitation device, mixing time 60min, pre-emulsification solution is made, for use in speed of agitator 200rad/min；
The pre-emulsification solution that step 4 prepares is slowly dropped to step 3 under conditions of heating stirring and prepares by step 5
Tapioca mixed liquor in, heating temperature be 55 DEG C, speed of agitator 200rad/min, the NaOH that a concentration of 10wt% is added dropwise it is molten
After liquid regulation system pH is 8,50min is stood, esterification modification Cassava starch adhesive is obtained；
Step 6, weighed according to parts by weight 9 parts of isocyanates, 1.5 parts of antioxidant, 2 parts of fire retardant, 0.2 part
Esterification modification Cassava starch adhesive prepared by light stabilizer, 1 part of ultra-violet absorber, 90 parts of step 4, in the item of stirring
Esterification modification para arrowroot is added in load weighted isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber 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 implementation mode seven：
A kind of hot setting type esterification modification Cassava starch adhesive, the hot setting type esterification modification tapioca
Adhesive is mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber
Be made, parts by weight be respectively 90 parts of 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 ultra-violet absorber, wherein the ingredient of Modified Oxidize Starth Adhesive stick include wood
Sweet potato starch, polyvinyl alcohol, lauryl sodium sulfate, dodecenylsuccinic acid acid anhydride.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the Modified Oxidize Starth Adhesive
The parts by weight of tapioca are 100 in stick, the parts by weight of polyvinyl alcohol are 8 parts, the parts by weight of lauryl sodium sulfate
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, the tapioca are configured to
Tapioca lotion, a concentration of 35wt% of the tapioca lotion.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the polyvinyl alcohol is with preparation
At poly-vinyl alcohol solution, a concentration of 12wt% of the poly-vinyl alcohol solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the dodecenylsuccinic acid
Acid anhydride is configured to dodecenylsuccinic acid anhydride solution, a concentration of 27wt% of the dodecenylsuccinic acid anhydride solution.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the antioxidant include 2,6-
Di-t-butyl -4- cresols and the double lauryls of thio-2 acid, 2,6-di-tert-butyl-4-methylphenol 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, the fire retardant is BDP.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the light stabilizer is 4- benzene
Formyloxy -2,2,6,6- tetramethyl piperidines.
Hot setting type esterification modification Cassava starch adhesive described in present embodiment, the ultra-violet absorber are
2-hydroxy-4-n-octoxybenzophenone.
Specific implementation mode eight：
The preparation method of hot setting type esterification modification Cassava starch adhesive according to specific implementation mode seven, packet
Include following steps：
Step 1, the tapioca that 100 parts are weighed according to parts by weight, parts by weight are added into load weighted tapioca
Number is 156 parts of distilled water, is placed on magnetic force heating stirrer and carries out heating stirring, 40 DEG C of heating temperature, mixing time
15min, speed of agitator 500rad/min obtain tapioca lotion, maintain the temperature at 40 DEG C, for use；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reaction kettle with blender, to weighing
Polyvinyl alcohol in parts by weight are added is 53 parts of distilled water, be warming up to 90 DEG C under stirring conditions, mixing time
10min, speed of agitator 500rad/min after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, for use；
Step 3, the tapioca lotion for preparing step 1 are added in the poly-vinyl alcohol solution of step 2 preparation, in temperature
Degree is 40 DEG C, under conditions of speed of agitator 200rad/min, and the NaOH solution regulation system pH that a concentration of 10wt% is added dropwise is 8,
Retention time 30min obtains tapioca mixed liquor；
Step 4, the lauryl sodium sulfate 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 into load weighted dodecenylsuccinic acid acid anhydride and is configured to 25wt% laurylene base fourths
Load weighted lauryl sodium sulfate is added in dodecenylsuccinic acid anhydride solution diacid anhydride solution, is placed into magnetic force heating
It is stirred on blender, mixing time 60min, pre-emulsification solution is made, for use in speed of agitator 200rad/min；
The pre-emulsification solution that step 4 prepares is slowly dropped to step 3 under conditions of heating stirring and prepares by step 5
Tapioca mixed liquor in, heating temperature be 55 DEG C, speed of agitator 200rad/min, the NaOH that a concentration of 10wt% is added dropwise it is molten
After liquid regulation system pH is 9,50min is stood, esterification modification Cassava starch adhesive is obtained；
Step 6, weighed according to parts by weight 7 parts of isocyanates, 1.5 parts of antioxidant, 2 parts of fire retardant, 0.2 part
Esterification modification Cassava starch adhesive prepared by light stabilizer, 1 part of ultra-violet absorber, 90 parts of step 4, in the item of stirring
Esterification modification para arrowroot is added in load weighted isocyanates, antioxidant, fire retardant, light stabilizer, ultra-violet absorber 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 implementation mode one to embodiment eight is applied
Glue suppresses three layers of poplar plywood under heat.The sheet of 120 DEG C, 3~4MPa of pressure of hot pressing temperature, preparation is placed for 24 hours
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 glued board.Examination
Part size grows 100 ± 1mm, and wide 25 ± 1mm, shear plane 25mm, specific sawing shape and size are as shown in attached drawing 1, attached drawing 2.
By the physico-chemical property of hot setting type esterification modification starch adhesive prepared by specific implementation mode two, four, six, eight
And mechanics properties testing result is in the following table 1.
The performance test of 1 hot setting type esterification modification Cassava starch adhesive of table
In the above test, the test of prepared esterification Cassava starch adhesive viscosity and solid 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《Glued board
Strength detection》, 3h will be impregnated in the water of the glued board immersion (63 ± 3) DEG C of the adhesive compacting in table 1, examination is tested under hygrometric state
Part stretches bonding strength.
The wet shape bonding strength of gained is satisfied by the national II class Strength of Plywood (>=0.7MPa) of GBT 9846-2015 in table,
So the esterification modification starch adhesive prepared by the present invention, bonding strength is completely up to standard, function admirable.
Claims (5)
1. a kind of hot setting type esterification modification Cassava starch adhesive, it is characterised in that：The hot setting type esterification changes
Property Cassava starch adhesive mainly by Modified Oxidize Starth Adhesive stick, isocyanates, antioxidant, fire retardant, light stabilizer, purple
Ultraviolet absorbers are made, and parts by weight are respectively 80~100 parts of Modified Oxidize Starth Adhesive stick, 7~12 parts of isocyanic acid
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 light
The ingredient of absorbent, wherein Modified Oxidize Starth Adhesive stick includes tapioca, polyvinyl alcohol, lauryl sodium sulfate, 12
Enetutanedioic acid anhydride；
The parts by weight of tapioca are the parts by weight of 70~100, polyvinyl alcohol in the Modified Oxidize Starth Adhesive stick
Parts by weight for 5.6~8 parts, lauryl sodium sulfate are 2~3 parts, the parts by weight of dodecenylsuccinic acid acid anhydride are 4~10
Part, starch esterification pH is 8~10；
The antioxidant includes 2,6-di-tert-butyl-4-methylphenol and the double lauryls of thio-2 acid, 2,6- di-t-butyl -4- first
The mass ratio of phenol and the double lauryls of thio-2 acid is 2:1；
The fire retardant is BDP；
The light stabilizer is 4- benzoyloxys -2,2,6,6- tetramethyl piperidines；
The ultra-violet absorber is 2-hydroxy-4-n-octoxybenzophenone.
2. hot setting type esterification modification Cassava starch adhesive according to claim 1, it is characterised in that：The wood
Sweet potato starch is configured to tapioca lotion, a concentration of 35~42wt% of the tapioca lotion.
3. hot setting type esterification modification Cassava starch adhesive according to claim 1 or 2, it is characterised in that：It is described
Polyvinyl alcohol be configured to poly-vinyl alcohol solution, a concentration of 10~15wt% of the poly-vinyl alcohol solution.
4. hot setting type esterification modification Cassava starch adhesive according to claim 1 or 2, it is characterised in that：It is described
Dodecenylsuccinic acid acid anhydride be configured to dodecenylsuccinic acid anhydride solution, the concentration of the dodecenylsuccinic acid anhydride solution
For 17~27wt%.
5. the preparation method of the hot setting type esterification modification Cassava starch adhesive described in a kind of one of claim 1-4,
It is characterized in that：Include the following steps：
Step 1, the tapioca that 70~100 parts are weighed according to parts by weight, parts by weight are added into load weighted tapioca
Number is 138~186 parts of distilled water, is placed on magnetic force heating stirrer and carries out heating stirring, 40 DEG C of heating temperature, when stirring
Between 10~30min, 200~500rad/min of speed of agitator obtains tapioca lotion, maintains the temperature at 40 DEG C, for use；
Step 2, the polyvinyl alcohol for weighing 8 parts according to parts by weight are placed in the reaction kettle with blender, to load weighted poly-
It is 46~72 parts of distilled water that parts by weight are added in vinyl alcohol, is warming up to 90 DEG C under stirring conditions, mixing time 5~
10min, 200~500rad/min of speed of agitator after polyvinyl alcohol is completely dissolved, are cooled to 40 DEG C, for use；
Step 3, the tapioca lotion for preparing step 1 are added in the poly-vinyl alcohol solution of step 2 preparation, are in temperature
40 DEG C, under conditions of 200~500rad/min of speed of agitator, the NaOH solution regulation system pH that a concentration of 10wt% is added dropwise is 8,
Retention time 30min obtains tapioca mixed liquor；
Step 4 weighs 2~3 parts of lauryl sodium sulfate, 4~10 parts of dodecenylsuccinic acid according to parts by weight respectively
The distilled water that parts by weight are 18~29 parts is added into load weighted dodecenylsuccinic acid acid anhydride and is configured to laurylene base fourth for acid anhydride
Load weighted lauryl sodium sulfate is added in dodecenylsuccinic acid anhydride solution diacid anhydride solution, is placed into magnetic force heating
It is stirred on blender, 30~60min of mixing time, 200~500rad/min of speed of agitator is made pre-emulsification solution, waits for
With；
The pre-emulsification solution that step 4 prepares is slowly dropped to wood prepared by step 3 by step 5 under conditions of heating stirring
In sweet potato starch mixed liquor, heating temperature is 55 DEG C, and the NaOH of a concentration of 10wt% is added dropwise in 100~200rad/min of speed of agitator
Solution regulation system pH=8,9,10,50min is stood, esterification modification Cassava starch adhesive is obtained；
Step 6 weighs 7~12 parts of isocyanates, 0.5~1.5 part of antioxidant, 0.5~2 part fire-retardant according to parts by weight
Esterification prepared by agent, 0.02~0.2 part of light stabilizer, 0.5~1 part of ultra-violet absorber, 80~100 parts of step 4 changes
Property Cassava starch adhesive, under stirring conditions by load weighted isocyanates, antioxidant, fire retardant, light stabilizer, ultraviolet
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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1673304A (en) * | 2005-02-07 | 2005-09-28 | 时君友 | Water-thinned isocyanate adhesive with corn starch as main material and its prepn process |
| CN101220248A (en) * | 2007-11-30 | 2008-07-16 | 东北农业大学 | Wood substance material adhesion agent manufactured with corn starch as main material and manufacturing method thereof |
| CN101870738A (en) * | 2009-04-23 | 2010-10-27 | 天津大学 | Alkyl acid esterified glutinous rice flour and preparation method as well as application thereof |
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| WO2003035740A1 (en) * | 2001-10-24 | 2003-05-01 | Temple-Inland Forest Products Corporation | Saccharide-based resin for the preparation of composite products |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1673304A (en) * | 2005-02-07 | 2005-09-28 | 时君友 | Water-thinned isocyanate adhesive with corn starch as main material and its prepn process |
| CN101220248A (en) * | 2007-11-30 | 2008-07-16 | 东北农业大学 | Wood substance material adhesion agent manufactured with corn starch as main material and manufacturing method thereof |
| CN101870738A (en) * | 2009-04-23 | 2010-10-27 | 天津大学 | Alkyl acid esterified glutinous rice flour and preparation method as well as application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 热压型淀粉基水性异氰酸酯木材胶黏剂的研制;陈晓波等;《东北林业大学学报》;20080725;第36卷(第7期);第78-90页 * |
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