CN103265920B - Method for preparing composite modified environmentally-friendly water-based phenolic resin adhesive - Google Patents
Method for preparing composite modified environmentally-friendly water-based phenolic resin adhesive Download PDFInfo
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- CN103265920B CN103265920B CN201310218739.5A CN201310218739A CN103265920B CN 103265920 B CN103265920 B CN 103265920B CN 201310218739 A CN201310218739 A CN 201310218739A CN 103265920 B CN103265920 B CN 103265920B
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Abstract
The invention discloses a method for preparing a composite modified environmentally-friendly water-based phenolic resin adhesive. Phenolic resin is compositely modified by adopting sucrose and organic silicon, the molecular weight of the resin is improved by using the polyhydroxy cross-linked structure of the sucrose, and the aim of improving the adhesive property of the resin is fulfilled, so that the product has high flexibility and high adhesive strength; meanwhile, formaldehyde is adopted and the solid formaldehyde is reacted with phenol, so that redundant moisture is not required to be vacuumized, and the solid content of the synthesized water-soluble phenolic resin meets the requirement. Moreover, the preparation method is simple and easy to operate.
Description
Technical field
The present invention relates to a kind of preparation method of sizing agent, particularly a kind of preparation method adopting the resol resins sizing agent of composite modifier modification.
Background technology
Resol (Phenol-fomaldehyde Resin), at first by Germany scientist Bayer, was obtained by formaldehyde and phenol reactant in 1872.1909, the patent of the phenolic resin adhesive of American scientist Baekeland, for the industrialization of resol is laid a good foundation.In adhesive made of synthetic resin field, resol, with its good weathering resistance, water tolerance, temperature tolerance and bond strength high, is widely used in coating, friction materials, insulating material, moulding compound etc.In order to overcome the intrinsic defect of resol, the performance and application scope of further raising resol, meet the needs of hi-tech development, many researchers have carried out large quantifier elimination to resol, the toughness of modified phenolic resins, improve mechanical property and resistance toheat, improve processing performance and become domestic and international study hotspot.
Resol is the reaction product of phenol or fortified phenol and formaldehyde.Change the kind of phenol and aldehyde, the amount ratio of phenol, the kind of catalyzer and consumption, reaction times and temperature, then it is all not identical to react the product generated.Important commodity phenol comprises phenol C
6h
5oH, cresylol CH
3c
6h
4oH, xylenol (CH
3)
2c
6h
3oH and p-tert-butylphenol etc.The amount of phenol used is than the kind with catalyzer, and decide resol is phenol end group or methylol end group.Phenol end group type resol is often called " linear phenolic resin " or " two step type resins "; This resin is not heat reactivity (unless adding more formaldehyde in addition), and they are generally with hexamethylenetetramine crosslinking curing in a heated condition.If molecular chain-end is methylol, be then called " resole " or " one step type resin "; This resin is heat reactivity, namely curable in a heated condition, forms thermoset reticulated structure [unless (such as adopting p-tert-butylphenol) is closed in advance in one of ortho position of phenol or contraposition].Two step type resins are prepared under phenol excessive [namely higher n(phenol)/n(catalyzer) ratio] exists with an acidic catalyst; One step type resin is prepared under aldehyde excessive [namely lower n(phenol)/n(catalyzer) ratio] exists with basic catalyst.Resol resins comprises water soluble phenol resin (mainly A stage resin) and water dispersible resol two class of low relative molecular mass, and the latter can be made up of the multiple resol comprising linear phenolic resin, and more stable.
In recent years, along with the more intensification people studied resol, many performances of resol are improved, also makes the range of application of phenolic resin adhesive more extensive.Believe people's deepening continuously to phenolic resin adhesive modification, corresponding transformed lines show also can emerge in an endless stream, thus the Application Areas of phenolic resin adhesive is constantly expanded.
Summary of the invention
The object of the invention is the defect overcoming existing phenolic resin adhesive, a kind of preparation method adopting the environment-friendly type aqueous phenolic resin adhesive of composite modifier modification is provided.
In order to realize above goal of the invention, the present invention by the following technical solutions: a kind of preparation method of composite modified environmental protection type resol resins sizing agent, comprises the following steps:
(1) raw material is prepared by following mass fraction: phenol 40 parts; 20 parts, formaldehyde; Solid formaldehyde 30 ~ 80 parts; Organosilicon 3 ~ 6 parts; Sucrose 1 ~ 2 part; Catalyzer 1 ~ 2 part;
(2) in phenol, add catalyzer, be warmed up to 40 DEG C, add organosilicon and sucrose, control temperature, between 40 ~ 50 DEG C, reacts 30min;
(3) add formaldehyde, control temperature is between 60 ~ 70 DEG C, and reaction 1h, continues to add solid formaldehyde, reaction 2h, cooling discharge after 80 ~ 90 DEG C of backflow 1h.
Described organosilicon is organosilicon 8427.
Described catalyzer is the mixture of sodium hydroxide and zinc oxide, and the mol ratio of sodium hydroxide and zinc oxide is 1 ~ 1.5:1.
The glued membrane of pure phenolic resin is firmly crisp, frangibility, have free formaldehyde and free-phenol release, and thermostability is poor, starts oxidation more than 200 DEG C in use procedure, can thermolysis to 340 ~ 360 DEG C.Adopt organosilicon to carry out modification to resol, the siloxane bond in organosilicon is incorporated in resol, the snappiness of resol can be improved, can thermotolerance be improved again.But organosilyl surface tension force and surface energy low, its intermolecular interaction force rate hydrocarbon polymer is much smaller, and with organism without cementability, smooth surface, so the bonding strength of modified synvaren can diminish.Adopt sucrose and organosilicon to carry out composite modified to resol, utilize sucrose poly-hydroxy crosslinking structure to improve molecular resin amount, reach the object of the adhesiveproperties improving resin, make product both have good snappiness, there is again higher bonding strength.
Conventional synthesis phenolic aldehyde all adopts phenol and formaldehyde reaction, because the massfraction of formaldehyde solution only has 37%, thus the water soluble phenol resin solid content synthesized is very low, the present invention adopts formaldehyde to use the method for solid formaldehyde simultaneously, do not need to vacuumize extraction excessive moisture, solid content can be made to meet the demands.
Major advantage of the present invention and beneficial effect are: adopt sucrose and organosilicon to carry out composite modified to resol, utilize sucrose poly-hydroxy crosslinking structure to improve molecular resin amount, reach the object of the adhesiveproperties improving resin, make product both have good snappiness, there is again higher bonding strength; Adopt formaldehyde to use solid formaldehyde and phenol reactant simultaneously simultaneously, do not need to vacuumize extraction excessive moisture, the water soluble phenol resin solid content of synthesis can be made to meet the demands.In addition preparation method of the present invention is simple, easy handling.
Embodiment
Below by embodiment, the present invention is further illustrated.
Embodiment one:
Raw material is prepared: phenol 40 parts by following mass fraction; 20 parts, formaldehyde; Solid formaldehyde 30 parts; Organosilicon 8,427 6 parts; Sucrose 1 part; 1 part, sodium hydroxide, 1 part, zinc oxide;
In phenol, add catalyzer, be warmed up to 40 DEG C, add organosilicon 8427 and sucrose, control temperature, between 40 ~ 50 DEG C, reacts 30min;
Add formaldehyde, control temperature is between 60 ~ 70 DEG C, and reaction 1h, continues to add solid formaldehyde, reaction 2h, cooling discharge after 80 ~ 90 DEG C of backflow 1h.
Embodiment two:
Raw material is prepared: phenol 40 parts by following mass fraction; 20 parts, formaldehyde; Solid formaldehyde 40 parts; Organosilicon 8,427 5 parts; Sucrose 2 parts; 1.2 parts, sodium hydroxide, 0.6 part, zinc oxide;
In phenol, add catalyzer, be warmed up to 40 DEG C, add organosilicon 8427 and sucrose, control temperature, between 40 ~ 50 DEG C, reacts 30min;
Add formaldehyde, control temperature is between 60 ~ 70 DEG C, and reaction 1h, continues to add solid formaldehyde, reaction 2h, cooling discharge after 80 ~ 90 DEG C of backflow 1h.
Embodiment three:
Raw material is prepared: phenol 40 parts by following mass fraction; 20 parts, formaldehyde; Solid formaldehyde 50 parts; Organosilicon 8,427 3 parts; Sucrose 2 parts; 0.5 part, sodium hydroxide, 0.5 part, zinc oxide;
In phenol, add catalyzer, be warmed up to 40 DEG C, add organosilicon 8427 and sucrose, control temperature, between 40 ~ 50 DEG C, reacts 30min;
Add formaldehyde, control temperature is between 60 ~ 70 DEG C, and reaction 1h, continues to add solid formaldehyde, reaction 2h, cooling discharge after 80 ~ 90 DEG C of backflow 1h.
Embodiment four:
Raw material is prepared: phenol 40 parts by following mass fraction; 20 parts, formaldehyde; Solid formaldehyde 80 parts; Organosilicon 8,427 4 parts; Sucrose 1 part; 0.8 part, sodium hydroxide, 0.8 part, zinc oxide;
In phenol, add catalyzer, be warmed up to 40 DEG C, add organosilicon 8427 and sucrose, control temperature, between 40 ~ 50 DEG C, reacts 30min;
Add formaldehyde, control temperature is between 60 ~ 70 DEG C, and reaction 1h, continues to add solid formaldehyde, reaction 2h, cooling discharge after 80 ~ 90 DEG C of backflow 1h.
Performance test:
(1) free formaldehyde content: utilize acetylacetone method to detect free formaldehyde content according to GB18582;
(2) tensile-sbear strength: detect tensile shear strength according to GB/ T7124-2008;
(3) viscosity: measure at 20 DEG C according to GB/ T11175-2002 Shanghai balance equipment factory NDJ-7 type rotary viscometer;
(4) snappiness: tackiness agent No. 25 line rods gluing 2 on the aluminium foil of the wide 2cm of long 10cm back and forth, is dried at 60 DEG C, is cooled to room temperature and starts doubling experiment, calculate folds.To adularescent folding line occurs, every sample 5 data are averaged.
Test result shows, resol resins sizing agent free formaldehyde content is low to moderate 0.054%, and bonding strength is up to 8.2MPa, and viscosity is 124 ~ 132mPas, and snappiness is at about 10 times.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of application claims.
Claims (1)
1. a preparation method for composite modified environmental protection type resol resins sizing agent, is characterized in that comprising the following steps:
(1) raw material is prepared by following mass fraction: phenol 40 parts; 20 parts, formaldehyde; Solid formaldehyde 30 ~ 80 parts; Organosilicon 3 ~ 6 parts; Sucrose 1 ~ 2 part; Catalyzer 1 ~ 2 part;
(2) in phenol, add catalyzer, be warmed up to 40 DEG C, add organosilicon and sucrose, control temperature, between 40 ~ 50 DEG C, reacts 30min;
(3) add formaldehyde, control temperature is between 60 ~ 70 DEG C, and reaction 1h, continues to add solid formaldehyde, reaction 2h, cooling discharge after 80 ~ 90 DEG C of backflow 1h;
Described organosilicon is organosilicon 8427;
Described catalyzer is the mixture of sodium hydroxide and zinc oxide, and the mol ratio of sodium hydroxide and zinc oxide is 1 ~ 1.5:1.
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| CN201310218739.5A CN103265920B (en) | 2013-06-04 | 2013-06-04 | Method for preparing composite modified environmentally-friendly water-based phenolic resin adhesive |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103525237A (en) * | 2013-10-21 | 2014-01-22 | 陆君军 | Preparation process of aqueous phenolic resin environment-friendly paint |
| CN104945582A (en) * | 2014-03-27 | 2015-09-30 | 江苏奎泽机械工业有限公司 | Preparation method of composite modified environment-friendly metal corrugated pipe adhesive |
| CN104946180A (en) * | 2014-03-27 | 2015-09-30 | 江苏奎泽机械工业有限公司 | Compound modified environment-friendly adhesive for metal bellows |
| CN104630935B (en) * | 2015-03-16 | 2016-06-29 | 山东莱芜润达新材料有限公司 | A kind of preparation method of high-strength composite resin fiber |
| CN106753103A (en) * | 2016-12-16 | 2017-05-31 | 安徽建筑大学 | A kind of environment protection type high-strength water-soluble phenolic resin adhesive |
| CN110615879B (en) * | 2019-11-11 | 2022-12-02 | 山东京博木基材料有限公司 | Preparation method of water-soluble phenolic resin |
| CN114031374A (en) * | 2021-12-16 | 2022-02-11 | 江苏鑫驰新材料有限公司 | Low-calcium magnesium spinel carbon brick and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175969A (en) * | 1995-01-25 | 1998-03-11 | 佐治亚-太平洋树脂公司 | Aqueous phenolic resin dispersions |
| CN102108275A (en) * | 2011-01-22 | 2011-06-29 | 上海泰尔精蜡有限公司 | Composite modification method for phenolic resin adhesive |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1175969A (en) * | 1995-01-25 | 1998-03-11 | 佐治亚-太平洋树脂公司 | Aqueous phenolic resin dispersions |
| CN102108275A (en) * | 2011-01-22 | 2011-06-29 | 上海泰尔精蜡有限公司 | Composite modification method for phenolic resin adhesive |
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