CN104926982B - A kind of polymer composite being modified for sheet material and preparation method thereof - Google Patents
A kind of polymer composite being modified for sheet material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polymer composite being modified for sheet material and preparation method thereof, the raw material of the polymer composite is made up of the component of following parts by weight：296 parts of polymer monomer, 20 40 parts of modifying agent, 6 12 parts of protecting colloid, 1.5 3.0 parts of initiator, 300 600 parts of water, and for adjusting the acid solution and aqueous slkali of pH value；The polymer monomer is acrylic acid or one kind or their mixture in esters of acrylic acid；The modifying agent is silane coupler；The protecting colloid is one kind in sodium polymethacrylate, polyvinyl alcohol, nano-cellulose or sodium carboxymethylcellulose；The initiator is ammonium persulfate or potassium peroxydisulfate.It can be reacted in the polymer composite of the present invention being modified for sheet material with the calcium ion in sheet material, and be solidified into the excellent waterproof layer of water resistance, be the ideal material during sheet fabrication.
Description
Technical field
The present invention relates to high molecular polymer field, specifically relates to a kind of polymer composite applied to sheet material modification
And preparation method thereof.
Background technology
Water proofing property is one of main performance index of sheet fabrication product, therefore sheet material is generally advance in process
Certain processing is carried out, the amount of water is absorbed to limit the sheet material and contact with moisture, increases its validity period.Such as in heating plate
, it is necessary to be pre-processed to sheet material in process, it is set to be formed by curing waterproof layer.
Water-repellent paint is brushed on building surface, the chemical reaction shape of volatilization or two kinds of components through solvent or moisture
Into thin film, building surface is set to completely cut off with water, so as to play a part of waterproof, sealing.Formed after water-repellent paint is cured
Waterproofing membrane there is certain extensibility, elastoplasticity, crack resistance, impermeability and weatherability, waterproof can be played, anti-blend protection
Effect.
In recent years, with the fast development of China's sheet material material converted products, waterproof of the board industry to sheet fabrication product
Performance requirement also more and more higher.But the waterproofing layer thickness that in general water-repellent paint is formed is thin, intensity is weak, can not be resistant in water
The erosion of the erosions such as acid, alkali, causes premature leakage.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of macromolecule composite wood being modified for sheet material
Material and preparation method thereof, the polymer composite is mainly used in during sheet fabrication, passes through polymer composite
Reacted with the calcium ion in sheet material, be solidified into waterproof layer.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of polymer composite being modified for sheet material, its raw material include the component of following parts by weight：Polymer list
296 parts of body, modifying agent 20-40 parts, protecting colloid 6-12 parts, initiator 1.5-3.0 parts, water 300-600 parts, and for adjusting
The acid solution and aqueous slkali of pH value；
Wherein, the polymer monomer is acrylic acid or one kind or their mixture in esters of acrylic acid；It is described to change
Property agent is silane coupler；The protecting colloid is sodium polymethacrylate, polyvinyl alcohol, nano-cellulose or carboxymethyl cellulose
One kind in plain sodium；The initiator is ammonium persulfate or potassium peroxydisulfate.
Further, the esters of acrylic acid is methyl acrylate or ethyl acrylate.
The silane coupler is alkenyl silanes coupling agent or methacryloxypropyl silane coupling agent.
The acid solution is one kind in hydrochloric acid, citric acid, oxalic acid or carboxylic acid, but not limited to this.
The aqueous slkali is one kind in sodium hydroxide, potassium hydroxide, ammoniacal liquor or sodium carbonate, but not limited to this.
The water is deionized water or distilled water.
The dosage of the acid solution and aqueous slkali is regulation acid-base value to corresponding pH value.
The preparation method of the polymer composite of the present invention being modified for sheet material comprises the following steps：By weight
Weigh each component,
1) polymer monomer of polymer monomer total amount 19/20 and modifying agent are pre-mixed, obtain polymer monomer
It is stand-by with modified agent composition；
2) by protecting colloid and water input reactor, 80-90 DEG C of temperature is controlled, stirs 30-60min；
3) concentration is passed through into reactor and is 99% nitrogen or carbon dioxide, and adds acid solution regulation pH value=3-5；
4) continue the polymer monomer of the input polymer monomer total amount 1/20 into reactor, stir 15-20min；
5) initiator of polymer monomer total amount 1/20 is put into reactor, stirs 25-35min；
6) polymer monomer and modified agent composition and remaining initiator that step 1) obtains are added dropwise into reactor,
Time for adding is 5-8h；
7) and then it is cooled to 35-40 DEG C, it is 0.02-0.06MPa to be evacuated to reacting kettle inner pressure, stirs 1-2h；
8) continue vacuum in release reaction kettle and be cooled to 30 DEG C, adjust pH=7.0-8.0 with aqueous slkali, stir 20min,
Produce the polymer composite being modified for sheet material.
The present invention uses above technical scheme, by the way that acrylic acid or acrylic polymer monomer are mixed with modifying agent
After be copolymerized, obtain containing carboxyl and silanol structuring polymer composite.During sheet fabrication, sheet material is soaked in this
Invent in the polymer composite, the calcium ion in sheet material can be anti-with the carboxyl in polymer composite and silanol structure
Should, form chemical key connection and be solidified into waterproof layer.Its mechanism is the meeting in sheet material immersion process of organic polymeric emulsions particle
Sheet material hole is penetrated into, then dehydration is deformed as having cohesiveness and successional layers of elastomeric film in the drying process, is covered
In plate surface；Simultaneously in sheet material drying process, the carboxyl in polymer molecule also can be with calcium ion formationization with silanol structure
Key connection is learned, so that flexible polymer film mutually runs through with sheet material hardenite：Flexible polymer-filled is hard in sheet material
In the space for changing body, make sheet material hardenite finer and close；Sheet material hardenite is filled in polymer phase again, polymer is had more
Good outdoor durable and more preferable basic unit's adaptability, so as to form a firm and flexible waterproof layer in plate surface.
Present invention process is simple, easy for construction, safety and environmental protection, is the ideal material in water-proof sheet material process.
Embodiment
A kind of polymer composite being modified for sheet material, its raw material include the component of following parts by weight：Polymer list
296 parts of body, modifying agent 20-40 parts, protecting colloid 6-12 parts, initiator 1.5-3.0 parts, water 300-600 parts, and for adjusting
The acid solution and aqueous slkali of pH value；
Wherein, the polymer monomer is acrylic acid or one kind or their mixture in esters of acrylic acid；
The modifying agent is alkenyl silanes coupling agent or methacryloxypropyl silane coupling agent；
The protecting colloid is in sodium polymethacrylate, polyvinyl alcohol, nano-cellulose or sodium carboxymethylcellulose
It is a kind of；
The initiator is ammonium persulfate or potassium peroxydisulfate；
The acid solution is one kind in hydrochloric acid, citric acid, oxalic acid or carboxylic acid；
The aqueous slkali is one kind in sodium hydroxide, potassium hydroxide, ammoniacal liquor or sodium carbonate；
The water is deionized water or distilled water.
The preparation method of the polymer composite being modified for sheet material comprises the following steps：Weigh by weight each
Component,
1) polymer monomer of polymer monomer total amount 19/20 and modifying agent are pre-mixed, obtain polymer monomer
It is stand-by with modified agent composition；
2) by protecting colloid and water input reactor, 80-90 DEG C of temperature is controlled, stirs 30-60min；
3) concentration is passed through into reactor and is 99% nitrogen or carbon dioxide, and adds acid solution regulation pH value=3-5；
4) continue the polymer monomer of the input polymer monomer total amount 1/20 into reactor, stir 15-20min；
5) initiator of polymer monomer total amount 1/20 is put into reactor, stirs 25-35min；
6) polymer monomer and modified agent composition and remaining initiator that step 1) obtains are added dropwise into reactor,
Time for adding is 5-8h；
7) and then it is cooled to 35-40 DEG C, it is 0.02-0.06MPa to be evacuated to reacting kettle inner pressure, stirs 1-2h；
8) continue vacuum in release reaction kettle and be cooled to 30 DEG C, adjust pH=7.0-8.0 with aqueous slkali, stir 20min,
Produce the polymer composite being modified for sheet material.
The present invention is further described with reference to specific embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1
A kind of preparation method for the polymer composite being modified for sheet material comprises the following steps：
1) following each component is weighed by weight：296 parts of polymer monomer, 30 parts of modifying agent, 9 parts of protecting colloid, trigger
2 parts of agent, 450 parts of deionized water；
2) polymer monomer of polymer monomer total amount 19/20 and modifying agent are pre-mixed, obtain polymer monomer
It is stand-by with modified agent composition；
3) by protecting colloid and water input reactor, 80-90 DEG C of temperature is controlled, stirs 45min；
4) concentration is passed through into reactor and is 99% nitrogen or carbon dioxide, and adds acid solution regulation pH value=4；
5) continue the polymer monomer of the input polymer monomer total amount 1/20 into reactor, stir 18min；
6) initiator of polymer monomer total amount 1/20 is put into reactor, stirs 30min；
7) polymer monomer and modified agent composition and remaining initiator that step 2) obtains are added dropwise into reactor,
Time for adding is 6.5h；
8) 35 DEG C are cooled to and then, it is 0.04MPa to be evacuated to reacting kettle inner pressure, stirs 1.5h；
9) continue vacuum in release reaction kettle and be cooled to 30 DEG C, adjust pH=7.5 with aqueous slkali, stir 20min, produce
The polymer composite being modified for sheet material；
Wherein, the polymer monomer is acrylic acid, and the modifying agent is methacryloxypropyl silane coupling agent, described
Protecting colloid is sodium polymethacrylate, and the initiator is ammonium persulfate, and the acid solution is hydrochloric acid, and the aqueous slkali is hydrogen
Sodium oxide molybdena.
Embodiment 2
A kind of preparation method for the polymer composite being modified for sheet material comprises the following steps：
1) following each component is weighed by weight：296 parts of polymer monomer, 20 parts of modifying agent, 6 parts of protecting colloid, trigger
1.5 parts of agent, 300 parts of distilled water；
2) polymer monomer of polymer monomer total amount 19/20 and modifying agent are pre-mixed, obtain polymer monomer
It is stand-by with modified agent composition；
3) by protecting colloid and water input reactor, 80-90 DEG C of temperature is controlled, stirs 30min；
4) concentration is passed through into reactor and is 99% nitrogen or carbon dioxide, and adds acid solution regulation pH value=3；
5) continue the polymer monomer of the input polymer monomer total amount 1/20 into reactor, stir 15min；
6) initiator of polymer monomer total amount 1/20 is put into reactor, stirs 25min；
7) polymer monomer and modified agent composition and remaining initiator that step 2) obtains are added dropwise into reactor,
Time for adding is 5h；
8) 35 DEG C are cooled to and then, it is 0.02MPa to be evacuated to reacting kettle inner pressure, stirs 1h；
9) continue vacuum in release reaction kettle and be cooled to 30 DEG C, adjust pH=7.0 with aqueous slkali, stir 20min, produce
The polymer composite being modified for sheet material；
Wherein, the polymer monomer is methyl acrylate, and the modifying agent is alkenyl silanes coupling agent, the Protection glue
Body is polyvinyl alcohol, and the initiator is potassium peroxydisulfate, and the acid solution is citric acid, and the aqueous slkali is potassium hydroxide.
Embodiment 3
A kind of preparation method for the polymer composite being modified for sheet material comprises the following steps：
1) following each component is weighed by weight：296 parts of polymer monomer, 40 parts of modifying agent, 12 parts of protecting colloid, trigger
3.0 parts of agent, 600 parts of deionized water；
2) polymer monomer of polymer monomer total amount 19/20 and modifying agent are pre-mixed, obtain polymer monomer
It is stand-by with modified agent composition；
3) by protecting colloid and water input reactor, 80-90 DEG C of temperature is controlled, stirs 60min；
4) concentration is passed through into reactor and is 99% nitrogen or carbon dioxide, and adds acid solution regulation pH value=5；
5) continue the polymer monomer of the input polymer monomer total amount 1/20 into reactor, stir 20min；
6) initiator of polymer monomer total amount 1/20 is put into reactor, stirs 35min；
7) polymer monomer and modified agent composition and remaining initiator that step 2) obtains are added dropwise into reactor,
Time for adding is 8h；
8) 40 DEG C are cooled to and then, it is 0.06MPa to be evacuated to reacting kettle inner pressure, stirs 2h；
9) continue vacuum in release reaction kettle and be cooled to 30 DEG C, adjust pH=8.0 with aqueous slkali, stir 20min, produce
The polymer composite being modified for sheet material；
Wherein, the polymer monomer is ethyl acrylate, and the modifying agent is methacryloxypropyl silane coupling agent,
The protecting colloid is nano-cellulose, and the initiator is ammonium persulfate, and the acid solution is oxalic acid, and the aqueous slkali is ammonia
Water.
Embodiment 4
A kind of preparation method for the polymer composite being modified for sheet material comprises the following steps：
1) following each component is weighed by weight：296 parts of polymer monomer, 25 parts of modifying agent, 8 parts of protecting colloid, trigger
2.5 parts of agent, 400 parts of distilled water；
2) polymer monomer of polymer monomer total amount 19/20 and modifying agent are pre-mixed, obtain polymer monomer
It is stand-by with modified agent composition；
3) by protecting colloid and water input reactor, 80-90 DEG C of temperature is controlled, stirs 50min；
4) concentration is passed through into reactor and is 99% nitrogen or carbon dioxide, and adds acid solution regulation pH value=4；
5) continue the polymer monomer of the input polymer monomer total amount 1/20 into reactor, stir 15min；
6) initiator of polymer monomer total amount 1/20 is put into reactor, stirs 30min；
7) polymer monomer and modified agent composition and remaining initiator that step 2) obtains are added dropwise into reactor,
Time for adding is 7h；
8) and then it is cooled to 35-40 DEG C, it is 0.02-0.06MPa to be evacuated to reacting kettle inner pressure, stirs 2h；
9) continue vacuum in release reaction kettle and be cooled to 30 DEG C, adjust pH=7.5 with aqueous slkali, stir 20min, produce
The polymer composite being modified for sheet material；
Wherein, the polymer monomer is acrylic acid and ethyl acrylate, and its weight part ratio is 1:1；The modifying agent is
Methacryloxypropyl silane coupling agent, the protecting colloid are sodium carboxymethylcellulose, and the initiator is ammonium persulfate, institute
It is carboxylic acid to state acid solution, and the aqueous slkali is sodium carbonate.
Embodiment 5
A kind of polymer composite being modified for sheet material, its raw material include the component of following parts by weight：Polymer list
296 parts of body, 35 parts of modifying agent, 10 parts of protecting colloid, 1.5 parts of initiator, 500 parts of deionized water；
Wherein, the polymer monomer is acrylic acid and methyl acrylate, and its weight part ratio is 1:2；The modifying agent is
Alkenyl silanes coupling agent, the protecting colloid are sodium polymethacrylate, and the initiator is potassium peroxydisulfate, and the acid solution is
Hydrochloric acid, the aqueous slkali are sodium hydroxide, the same embodiment of preparation method of the polymer composite being modified for sheet material
1。
Embodiment 6
A kind of polymer composite being modified for sheet material, its raw material include the component of following parts by weight：Polymer list
296 parts of body, 35 parts of modifying agent, 10 parts of protecting colloid, 3.0 parts of initiator, 500 parts of distilled water；
Wherein, the polymer monomer is acrylic acid, methyl acrylate and ethyl acrylate, and its weight part ratio is 1:1:1；
The modifying agent is methacryloxypropyl silane coupling agent；The protecting colloid is polyvinyl alcohol；The initiator is over cure
Sour potassium；The acid solution is citric acid；The aqueous slkali is sodium carbonate, the polymer composite being modified for sheet material
Preparation method is the same as embodiment 2.
Experimental example
After the sheet material after polymer composite of the present invention processing is soaked into 3h in room temperature water, measure sheet material water suction
The sheet material of rate, wherein control group is handled without polymer composite, and result of the test is as follows：
| Group | Water absorption rate (%) |
| Control | 15.0 |
| Embodiment 1 | 1.0 |
| Embodiment 2 | 1.2 |
| Embodiment 3 | 1.0 |
| Embodiment 4 | 0.8 |
| Embodiment 5 | 0.9 |
| Embodiment 6 | 1.0 |
From result above, after soaking 3h in room temperature water, the water absorption rate of control group sheet material is 15%, and passes through and implement
Sheet material after example 1-6 polymer composite processing, its water absorption rate are less than 1.2%.Because answered through macromolecule of the present invention
Plate surface after condensation material processing forms firm and flexible waterproof layer, significantly improves the water resistance of sheet material.
Claims (1)
- A kind of 1. preparation method for the polymer composite being modified for sheet material, it is characterised in that：It comprises the following steps：1）Following each component is weighed by weight：296 parts of polymer monomer, 30 parts of modifying agent, 9 parts of protecting colloid, initiator 2 Part, 450 parts of deionized water；Wherein, the polymer monomer is acrylic acid, and the modifying agent is methacryloxypropyl silane coupling agent, the protection Colloid is sodium polymethacrylate, and the initiator is ammonium persulfate；2）The polymer monomer of polymer monomer total amount 19/20 and modifying agent are pre-mixed, obtain polymer monomer with changing Property agent composition, it is stand-by；3）By in protecting colloid and water input reactor, 80-90 DEG C of temperature is controlled, stirs 45min；4）Concentration is passed through into reactor and is 99% nitrogen, and adds hydrochloric acid solution regulation pH value=4；5）Continue to put into remaining polymer monomer into reactor, stir 18min；6）The initiator of polymer monomer total amount 1/20 is put into reactor, stirs 30 min；7）Polymer monomer and modified agent composition and remaining initiator that step 2) obtains are added dropwise into reactor, is added dropwise Time is 6.5 h；8）Then 35 DEG C are cooled to, it is 0.04MPa to be evacuated to reacting kettle inner pressure, stirs 1.5h；9）Continue vacuum in release reaction kettle and be cooled to 30 DEG C, adjust pH=7.5 with sodium hydroxide solution, stir 20 min, i.e., The polymer composite of sheet material modification must be used for.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1107693C (en) * | 1998-01-13 | 2003-05-07 | 江苏日出(集团)公司 | Polyacrylic water-proof emulsion |
| CN1166705C (en) * | 2001-04-23 | 2004-09-15 | 海城市西柳化学品有限公司 | Benzenepropane emulsion modified by silane as coupling agent and its preparing process and application |
| CN101328237B (en) * | 2007-06-18 | 2011-06-15 | 陕西邦希化工有限公司 | Preparation of cation surface sizing agent emulsion |
| DE102008008421B4 (en) * | 2008-02-09 | 2014-06-26 | Celanese Emulsions Gmbh | Process for the preparation of polymer dispersions, the dispersions containing them and their use |
| CN101550217A (en) * | 2009-05-12 | 2009-10-07 | 天津城市建设学院 | Method for preparing soap-free silicone-acrylic emulsion with core-shell structure |
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