CN103275660B - The preparation method of carbon nano-tube modification urea-formaldehyde resin adhesive - Google Patents
The preparation method of carbon nano-tube modification urea-formaldehyde resin adhesive Download PDFInfo
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- CN103275660B CN103275660B CN201310245276.1A CN201310245276A CN103275660B CN 103275660 B CN103275660 B CN 103275660B CN 201310245276 A CN201310245276 A CN 201310245276A CN 103275660 B CN103275660 B CN 103275660B
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Abstract
The invention discloses a kind of preparation method of carbon nano-tube modification urea-formaldehyde resin adhesive, carbon nanotube and nano titanium oxide is adopted to prepare urea-formaldehyde resin adhesive as properties-correcting agent, due to this special construction of carbon nanotube, make it can react with the free formaldehyde in urea-formaldehyde resin, thus reduce the burst size of free formaldehyde; Using nanometer titanium dioxide carbon as properties-correcting agent, not only can reduce the burst size of free formaldehyde, the bonding strength of urea-formaldehyde resin adhesive can also be strengthened.The preparation technology of urea-formaldehyde resin adhesive of the present invention is simple, easy handling.
Description
Technical field
The present invention relates to the preparation method that a kind of modified urea-formaldehyde resin glue sticks agent, particularly a kind of carbon nanotube and nano titanium oxide of adopting sticks the preparation method of agent as the modified urea-formaldehyde resin glue of properties-correcting agent.
Background technology
Urea-formaldehyde resin adhesive is the maximum adhesive made of synthetic resin of China's timber industry consumption, accounts for more than 60% of wood-processing industry sizing agent total flow, accounts for about 90% of wood-based plate glue consumption.Urea-formaldehyde resin adhesive has plurality of advantages, as higher Joint strength, high resistance to cold water performance, medium heat-proof water performance; Solidification rapidly; Good with water miscibility, easily modulation suitable viscosity and concentration etc.; But the basic reason that its consumption is large is that price advantage-it is cheapest in adhesive made of synthetic resin.But urea-formaldehyde resin adhesive and cementitious product thereof constantly can discharge formaldehyde in use journey, harmful, which greatly limits its use range.
Formaldehyde is the potential carcinogen matter of generally acknowledging in the world, and serious harm people's is healthy, causes immunologic dysfunction, liver injury, injury of lung and central nervous system to be affected, and can also cause fetal anomaly.The speed that finishing wood-based plate Free-formaldehyde evaporates from wood-based plate is comparatively slow, and indoor air formaldehyde content is exceeded standard for a long time.China has formulated ten national standards such as GB18580-2001 " interior architecture finishing material-wood-based plate and goods in burst size of methanal " thereof for this reason, and compulsory execution from 1 day July in 2002, this will realize the environmental protection of urea-formaldehyde resin artificial board.Present free formaldehyde in urea-formaldehyde resin content is general to be judged according to European standard, utilize the free formaldehyde content bored in empty method sheet material measurement, this judgement urea aldehyde Free-formaldehyde content of Ju, be divided into E1 level (< 10mg/100g), E2 level (< 30mg/100g), E3 level (< 60mg/100g), wherein E1 level and E2 level belong to environment-friendly type, and current China product mostly is, and E2, E3 level quality is anxious to be waited to improve.
Take urea-formaldehyde resin as the wood-based panel product of sizing agent, the reason to environment emitting formaldehyde in production and use procedure has: the free formaldehyde of failing thoroughly to react that the addition reaction stage at (1) resins synthesis initial stage causes due to reversible reaction; (2) the methyl ether key generated in resin polycondensation and curing reaction and methylol are in the decomposition of hot press period; (3) remaining after hot pressing formaldehyde key and the decomposition of methylol under environmental activity.Therefore, how to reduce artificial board formaldehyde burst size and become the focus of current research.
Properties-correcting agent refers to some performance in order to improve urea-formaldehyde resin adhesive, other additives added before the some of its building-up process or several stage or the use at glue.Urea-formaldehyde resin adhesive can relate to many performance issues special procured in actual production uses, therefore properties-correcting agent is also of a great variety.As softening agent and toughner can improve the fragility of glue-line; The mineral filler of metal-powder etc. can improve the mechanical property of sizing agent; Add the stress that flour can reduce adhesively bonded joint; Fire retardant can improve the flame resistivity of cementitious article.The above-mentioned additive added to reach different object all belongs to properties-correcting agent.The properties-correcting agent used to reduce urea-formaldehyde resin and goods toxicity thereof is wherein a kind of.
According to the practical situation of China's Wood-based Panel Production, whether the cost of properties-correcting agent is selected most important to producer.So when preparing Low Toxicity Modifiers for Urea-formaldehyde Resin Adhesive, except considering effectively to reduce except resin free formaldehyde content and goods free formaldehyde release thereof, a prior principle is that the cost of properties-correcting agent is unsuitable too high; In addition, add the glue after properties-correcting agent and can not make Wood-based Panel Production technique overcomplicated in use.
Summary of the invention
The object of the invention is to overcome the defect that existing urea-formaldehyde resin adhesive exists, provide a kind of preparation technology is simple, burst size of methanal is low modified urea-formaldehyde resin glue to stick the preparation method of agent.
In order to realize above goal of the invention, the present invention by the following technical solutions: a kind of preparation method of carbon nano-tube modification urea-formaldehyde resin adhesive, comprises the following steps:
(1) raw material is prepared by following mass fraction: methanol solution 30 ~ 40 parts; 20 ~ 30 parts, urea; Polyvinyl alcohol 30 ~ 40 parts; Carbon nanotube 5 ~ 10 parts; Nano titanium oxide 2 ~ 5 parts; Ammonium chloride 10 ~ 15 parts; P-aminophenol 2 ~ 5 parts;
(2) in methanol solution, add polyvinyl alcohol, stir and be heated to 40 DEG C, adjust ph, 7.5 ~ 8.5, adds the urea of 1/3, ammonium chloride and p-aminophenol, stirs and continues to be warming up to 80 DEG C, reaction 2h;
(3) adjust ph is 6.5 ~ 7.5, then adds the urea of 1/3, stirring reaction 2h; Adjust ph, 7.0 ~ 8.0, is cooled to the urea that 60 DEG C add 1/3 again, stirring reaction 2h;
(4) be cooled to room temperature, add carbon nanotube and nano titanium oxide stirring 30min, obtain carbon nano-tube modification urea-formaldehyde resin adhesive.
The formaldehyde content of described methanol solution is 37% ~ 40%, and methanol content is 4%.
Described Carbon nanotubes is multi-walled carbon nano-tubes, and external diametrical extent is 10 ~ 20nm, and length is 5 ~ 50 μm, adopts strong acid oxide treatment.
Described nano titanium oxide is anatase titanium dioxide, and median size is 30nm.
Since first carbon nanotube was found by Electronic Speculum expert professor Iijima of Japanese NEC from 1991, between the short more than ten years, the carbonaceous pipe of this nano-scale just causes the broad interest of the scientific circles such as global physics, chemistry and material.Due to special construction and excellent mechanics, electricity and optical property and its potential industrial value of carbon nanotube, make it become the study hotspot of the ambits such as chemistry, physics and material gradually, have people even it to be described as " Black Diamond of 21 century ".Carbon nanotube is the One-dimensional Quantum material with special construction (radial dimension is nanometer scale, and axial dimension can reach micron dimension), and have typical stratiform hollow structure feature, the two ends of general pipe have end cap to seal.The pipe shaft of carbon nanotube is director circle tubular construction, is made up of hexagonal carbon ring structure unit, and terminal cap moiety is the polygonized structure containing pentagon and hexagonal carbocyclic ring composition.Due to this special construction of carbon nanotube, make it can react with the free formaldehyde in urea-formaldehyde resin, thus reduce the burst size of free formaldehyde.
Nano titanium oxide is n-type semiconductor, because of its have that chemical property Ah is stable, strong, the anti-light cathodic corrosion of oxidation-reduction quality, indissoluble, nontoxic, cost is low, catalytic activity is high and be widely used.Using nanometer titanium dioxide carbon as properties-correcting agent, not only can reduce the burst size of free formaldehyde, the bonding strength of urea-formaldehyde resin adhesive can also be strengthened.
Major advantage of the present invention and beneficial effect are: adopt carbon nanotube and nano titanium oxide to prepare urea-formaldehyde resin adhesive as properties-correcting agent, due to this special construction of carbon nanotube, make it can react with the free formaldehyde in urea-formaldehyde resin, thus reduce the burst size of free formaldehyde; Using nanometer titanium dioxide carbon as properties-correcting agent, not only can reduce the burst size of free formaldehyde, the bonding strength of urea-formaldehyde resin adhesive can also be strengthened.The preparation technology of urea-formaldehyde resin adhesive of the present invention is simple, easy handling.
Embodiment
Below by embodiment, the present invention is further illustrated.
Embodiment one:
Raw material is prepared: methanol solution 30 parts by following mass fraction; 20 parts, urea; Polyvinyl alcohol 35 parts; Carbon nanotube 6 parts; Nano titanium oxide 2 parts; Ammonium chloride 15 parts; P-aminophenol 3 parts;
In methanol solution, add polyvinyl alcohol, stir and be heated to 40 DEG C, adjust ph, 7.5 ~ 8.5, adds the urea of 1/3, ammonium chloride and p-aminophenol, stirs and continues to be warming up to 80 DEG C, reaction 2h;
Adjust ph 6.5 ~ 7.5, then adds the urea of 1/3, stirring reaction 2h; Adjust ph, 7.0 ~ 8.0, is cooled to the urea that 60 DEG C add 1/3 again, stirring reaction 2h;
Be cooled to room temperature, add carbon nanotube and nano titanium oxide stirring 30min, obtain carbon nano-tube modification urea-formaldehyde resin adhesive.
Embodiment two:
Raw material is prepared: methanol solution 34 parts by following mass fraction; 30 parts, urea; Polyvinyl alcohol 38 parts; Carbon nanotube 10 parts; Nano titanium oxide 4 parts; Ammonium chloride 10 parts; P-aminophenol 5 parts;
In methanol solution, add polyvinyl alcohol, stir and be heated to 40 DEG C, adjust ph, 7.5 ~ 8.5, adds the urea of 1/3, ammonium chloride and p-aminophenol, stirs and continues to be warming up to 80 DEG C, reaction 2h;
Adjust ph 6.5 ~ 7.5, then adds the urea of 1/3, stirring reaction 2h; Adjust ph, 7.0 ~ 8.0, is cooled to the urea that 60 DEG C add 1/3 again, stirring reaction 2h;
Be cooled to room temperature, add carbon nanotube and nano titanium oxide stirring 30min, obtain carbon nano-tube modification urea-formaldehyde resin adhesive.
Embodiment three:
Raw material is prepared: methanol solution 35 parts by following mass fraction; 25 parts, urea; Polyvinyl alcohol 40 parts; Carbon nanotube 8 parts; Nano titanium oxide 3 parts; Ammonium chloride 13 parts; P-aminophenol 4 parts;
In methanol solution, add polyvinyl alcohol, stir and be heated to 40 DEG C, adjust ph, 7.5 ~ 8.5, adds the urea of 1/3, ammonium chloride and p-aminophenol, stirs and continues to be warming up to 80 DEG C, reaction 2h;
Adjust ph 6.5 ~ 7.5, then adds the urea of 1/3, stirring reaction 2h; Adjust ph, 7.0 ~ 8.0, is cooled to the urea that 60 DEG C add 1/3 again, stirring reaction 2h;
Be cooled to room temperature, add carbon nanotube and nano titanium oxide stirring 30min, obtain carbon nano-tube modification urea-formaldehyde resin adhesive.
Embodiment four:
Raw material is prepared: methanol solution 40 parts by following mass fraction; 30 parts, urea; Polyvinyl alcohol 32 parts; Carbon nanotube 5 parts; Nano titanium oxide 5 parts; Ammonium chloride 12 parts; P-aminophenol 2 parts;
In methanol solution, add polyvinyl alcohol, stir and be heated to 40 DEG C, adjust ph, 7.5 ~ 8.5, adds the urea of 1/3, ammonium chloride and p-aminophenol, stirs and continues to be warming up to 80 DEG C, reaction 2h;
Adjust ph 6.5 ~ 7.5, then adds the urea of 1/3, stirring reaction 2h; Adjust ph, 7.0 ~ 8.0, is cooled to the urea that 60 DEG C add 1/3 again, stirring reaction 2h;
Be cooled to room temperature, add carbon nanotube and nano titanium oxide stirring 30min, obtain carbon nano-tube modification urea-formaldehyde resin adhesive.
Resin traditional performance measures according to standard GB/T/T14074-93 " wood adhesive and the resin method of inspection thereof "; Plate property measures by standard GB/T/T9846-2004 " glued board "; Burst size of methanal measures by standard GB/T/T17657-1999 " wood-based plate instant noodles wood-based plate physicochemical property test method " and standard GB/T 18580-2001 " in indoor decorating and refurnishing materials wood-based plate machine goods Form aldehyde release limitation ".
Test result shows, modified urea-formaldehyde resin glue of the present invention sticks the bonding strength of agent at 0.87 ~ 1.12MPa, burst size of methanal at 5.7 ~ 6.6mg/L, far below national standard.
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 (3)
1. a preparation method for carbon nano-tube modification urea-formaldehyde resin adhesive, is characterized in that comprising the following steps:
(1) raw material is prepared by following mass fraction: methanol solution 30 ~ 40 parts; 20 ~ 30 parts, urea; Polyvinyl alcohol 30 ~ 40 parts; Carbon nanotube 5 ~ 10 parts; Nano titanium oxide 2 ~ 5 parts; Ammonium chloride 10 ~ 15 parts; P-aminophenol 2 ~ 5 parts;
(2) in methanol solution, add polyvinyl alcohol, stir and be heated to 40 DEG C, adjust ph, 7.5 ~ 8.5, adds the urea of 1/3, ammonium chloride and p-aminophenol, stirs and continues to be warming up to 80 DEG C, reaction 2h;
(3) adjust ph is 6.5 ~ 7.5, then adds the urea of 1/3, stirring reaction 2h; Adjust ph, 7.0 ~ 8.0, is cooled to the urea that 60 DEG C add 1/3 again, stirring reaction 2h;
(4) be cooled to room temperature, add carbon nanotube and nano titanium oxide stirring 30min, obtain carbon nano-tube modification urea-formaldehyde resin adhesive;
The formaldehyde content of described methanol solution is 37% ~ 40%, and methanol content is 4%.
2. the preparation method of carbon nano-tube modification urea-formaldehyde resin adhesive according to claim 1, is characterized in that: described carbon nanotube is multi-walled carbon nano-tubes, and external diametrical extent is 10 ~ 20nm, and length is 5 ~ 50 μm, adopts strong acid oxide treatment.
3. the preparation method of carbon nano-tube modification urea-formaldehyde resin adhesive according to claim 1, is characterized in that: described nano titanium oxide is anatase titanium dioxide, and median size is 30nm.
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| US8426501B1 (en) * | 2010-05-13 | 2013-04-23 | Stc.Unm | Generation of polymer concretes incorporating carbon nanotubes |
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| US8426501B1 (en) * | 2010-05-13 | 2013-04-23 | Stc.Unm | Generation of polymer concretes incorporating carbon nanotubes |
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| 连海兰等.二氧化钛在脲醛树脂胶黏剂中的应用研究.《林产工业》.2011,第38卷(第6期), * |
| 铁昆灵.多壁碳纳米管的表面修饰及改性脲醛树脂的研究.《万方硕士论文数据库》.2012, * |
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